## Online First

Articles in press have been peer-reviewed and accepted, which are not yet assigned to volumes/issues, but are citable by Digital Object Identifier (DOI).
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The generalized quantum master equation (GQME) provides a general and exact approach for simulating the reduced dynamics in open quantum system where a quantum system is embedded in a quantum environment. Dynamics of open quantum systems is important in excitation energy, charge, and quantum coherence transfer as well as reactive photochemistry. The system is usually chosen to be the interested degrees of freedom such as the electronic states in light-harvesting molecules or tagged vibrational modes in a condensed-phase system. The environment is also called the bath, whose influence on the system has to be considered, and for instance can be described by the GQME formalisms using the projection operator technique. In this review, we provide a heuristic description of the development of two canonical forms of GQME, namely the time-convoluted Nakajima-Zwanzig form (NZ-GQME) and the time-convolutionless form (TCL-GQME). In the more popular NZ-GQME form, the memory kernel serves as the essential part that reflects the non-Markovian and non-perturbative effects, which gives formally exact dynamics of the reduced density matrix. We summarize several schemes to express the projection-based memory kernel of NZ-GQME in terms of projection-free time correlation function inputs that contain molecular information. In particular, the recently proposed modified GQME approach based on NZ-GQME partitions the Hamiltonian into a more general diagonal and off-diagonal parts. The projection-free inputs in the above-mentioned schemes expressed in terms of different system-dependent time correlation functions can be calculated via numerically exact or approximate dynamical methods. We hope this contribution would help lower the barrier of understanding the theoretical pillars for GQME-based quantum dynamics methods and also envisage that their combination with the quantum computing techniques will pave the way for solving complex problems related to quantum dynamics and quantum information that are currently intractable even with today's state-of-the-art classical supercomputers.
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Mixed halide perovskites (MHPs) are a class of semiconductor material of great promise for many optoelectronic applications due to their outstanding photophysical properties. Understanding and tailoring the photogenerated carrier dynamics is essential for the further improvement of perovskite performance. Herein, we report a study about the carrier transport and interfacial charge transfer dynamics in Br-gradient MAPbI<sub>3-x</sub>Br<sub>x</sub> perovskite thin films prepared by surface ion-exchange method. Driven by the bandgap gradient in MAPbI<sub>3-x</sub>Br<sub>x</sub> films, the accelerated internal hole transport and enhanced interfacial extraction efficiency were both observed. Meanwhile, the interfacial electron transfer was also found to be evidently facilitated due to the surface modification during post-treatment. Our findings suggest the possibility of simultaneous acceleration of interfacial electron and hole transfer processes in halide perovskite films via surface post-treatment technique, which is of great importance in further improving the PCE of perovskite solar cells.
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In the past few years, the renormalized excitonic model (REM) approach was developed as an efficient low-scaling ab initio excited state method, which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings. In this work, we further extend the REM calculations for the evaluations of first-order molecular properties (e.g. charge population and transition dipole moment) of delocalized ionic or excited states in molecular aggregates, through generalizing the effective Hamiltonian theory to effective operator representation. Results from the test calculations for four different kinds of one dimensional (1D) molecular aggregates (ammonia, formaldehyde, ethylene and pyrrole) indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.
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Conductive ionic hydrogels (CIH) have been widely studied for the development of stretchable electronic devices, such as sensors, electrodes and actuators. Most of these CIH are made into 3D or 2D shape, while 1D CIH (hydrogel fibers) is often difficult to make, because of the low mechanical robustness of common CIH. Herein, we use gel spinning method to prepare a robust CIH fiber with high strength, large stretchability and good conductivity. The robust CIH fiber is drawn from the composite gel of sodium polyacrylate (PAAS) and sodium carboxymethyl cellulose (CMC). In the composite CIH fiber, the soft PAAS presents good conductivity and stretchability, while the rigid CMC significantly enhances the strength and toughness of the PAAS/CMC fiber. To protect the conductive PAAS/CMC fiber from damage by water, a thin layer of hydrophobic polymethyl acrylate (PMA) or polybutyl acrylate (PBA) was coated on the PAAS/CMC fiber as a water-resistant and insulating cover. The obtained PAAS/CMC-PMA and PAAS/CMC-PBA CIH fibers present high tensile strength (up to 28 MPa), high tensile toughness (up to 43 MJ m-3), and good electrical conductivity (up to 0.35 S m-1), which are useful for textile-based stretchable electronic devices.
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The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides. Density functional theory plus the Hubbard $U$ correction (DFT+$U$) and constrained density functional theory (cDFT) are often used to obtain the transfer properties for small polarons. In this work we have implemented the cDFT plus the Hubbard $U$ correction method in the projector augmented wave (PAW) framework, and applied it to study polaron transfer in the bulk phases of \ce{TiO2}. We have confirmed that the parameter $U$ can have significant impact on theoretical prediction of polaronic properties. It was found that using the Hubbard $U$ calculated by the cDFT method with the same orbital projection as used in DFT+$U$, one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of \ce{TiO2} in good agreement with experiment. This work indicates that the cDFT+$U$ method with consistently evaluated $U$ is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.
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Coherent vibrational dynamics can be observed in atomically precise gold nanoclusters using femtosecond time-resolved pump-probe spectroscopy. It can not only reveal the coupling between electrons and vibrations, but also reflect the mechanical and electronic properties of metal nanoclusters, which holds potential applications in biological sensing and mass detection. Here, we investigated the coherent vibrational dynamics of Au25(SR)18 nanoclusters by ultrafast spectroscopy and revealed the origins of these coherent vibrations by analyzing their frequency, phase and probe wavelength distributions. Strong coherent oscillations with frequency of 40 cm-1 and 80 cm-1 can be reproduced in the excited state dynamics of Au25(SR)18, which should originate from acoustic vibrations of the Au13 metal core. Phase analysis on the oscillations indicates that the 80 cm-1 mode should arise from the frequency modulation of the electronic states while the 40 cm-1 mode should originate from the amplitude modulation of the dynamic spectrum. Moreover, it is found that the vibration frequencies of Au25(SR)18 obtained in pump-probe measurements are independent of the surface ligands so that they are intrinsic properties of the metal core. These results are of great value to understand the electron-vibration coupling of metal nanoclusters.
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MXenes, a new family of two-dimensional (2D) materials, have received extensive interest due to their fascinating physicochemical properties, such as outstanding light-to-heat conversion efficiency. However, the photothermal conversion mechanism of MXenes is still poorly understood. Here, by using femtosecond visible and mid-infrared transient absorption spectroscopy, the electronic energy dissipation dynamics of MXene (Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>) nanosheets dispersed in various solvents have been carefully studied. Our results indicate that the lifetime of photoexcited MXene is strongly dependent on the surrounding environment. Especially, the interfacial electron-vibration coupling between the MXene nanosheets and the adjacent solvent molecules is directly observed following the ultrafast photoexcitation of MXene. It suggests that the interfacial interactions at the MXene-solvent interface play a critical role in the ultrafast energy transport dynamics of MXene, which offers a potentially feasible route for tailoring the light conversion properties of 2D systems.
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[4Fe-4S]-dependent radical S-adenosylmethionine (SAM) proteins are a superfamily of oxidoreductases that can catalyze a series of challenging transformations using the common 5-dAdo radical intermediate. Although the structures and functions of radical SAM (RS) enzymes have been extensively studied, the electronic state-dependent reactions of the [4Fe-4S] clusters in these enzymes are still elusive. Herein we performed QM/MM calculations to elucidate the electronic state-dependent reactivity of the [4Fe-4S] cluster in pyruvate-formate lyase activating enzyme (PFL-AE). Our calculations show that the electronic state-dependent SAM activation by the [4Fe-4S] clusters in RS enzyme is determined by both the super-exchange and exchange-enhanced reactivities. The super-exchange coupling in the [4Fe-4S] cluster favors the antiferromagnetic coupling between two neighbouring pairs, which results in the α-electron rather than the β-electron donation from the [4Fe-4S]1+ cluster toward the SAM activation. Meanwhile, in the most favorable electronic state for the reductive cleavage of S−C5’, Fe4 would donate its α-electron to gain the maximum exchange interactions in the Fe4-block. Such super-exchange and exchange-enhanced reactivity could be the general principles for reactivities of [4Fe-4S] cluster in RS enzymes.
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The reaction H + SO2 → OH + SO is important in the combustion and atmospheric chemistry, as well as the interstellar medium. It also represents a typical complex-forming reaction with deep complexes, serving as an ideal candidate for testing various kinetics theories and providing interesting reaction dynamical phenomena. In this work, we reported a quasi−classical trajectory (QCT) study of this reaction on our previously developed accurate full-dimensional potential energy surface (PES). The experimental thermal rate coefficients over the temperature range 1400K ≤ T ≤ 2200K were well reproduced. For the reactant SO2 being sampled at the ground ro-vibrational state, the calculated integral cross sections (ICSs) increased slightly along the collision energy ranging from 31.0 to 40.0 kcal mol−1, and then became essentially flat at the collision energy within 40 – 55 kcal mol−1. The product angular distributions are almost symmetric with nearly identical backward-forward double peak structure. The products OH and SO vibrational state distributions were also analyzed.
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LASP (Large-scale Atomistic Simulation with neural network Potential) software developed by our group since 2018 is a powerful platform (www.lasphub.com) for performing atomic simulation of complex materials. The software integrates the neural network (NN) potential technique with the global potential energy surface exploration method, and thus can be utilized widely for structure prediction and reaction mechanism exploration. Here we introduce our recent update on the LASP program version 3.0, focusing on the new functionalities including the advanced NN training based on multi-network framework, the newly-introduced S7 and S8 power type structure descriptor (PTSD). These new functionalities are designed to further improve the accuracy of potentials and accelerate the NN training for multiple-element systems. Taking Cu-C-H-O NN potential and a heterogeneous catalytic model as the example, we show that these new functionalities can accelerate the training of multi-element NN potential by using the existing single-network potential as the input. The obtained double-network potential CuCHO is robust in simulation and the introduction of S7 and S8 PTSDs can reduce the RMSE of energy by a factor of two.
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The kinetics of U(IV) produced by hydrazine reducting U(VI) with platinum as catalyst in nitric acid media was studied for revealing the reaction mechanism and optimizing the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The influence of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction were studied. Concurrently, the simulation of the reaction process was performed using density functional theory (DFT). The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid was below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as follows: –dc(UO22+)/dt) = kc0.5323(UO22+)c0.2074(N2H5+)c−0.2009(H+). When the temperature is 50°C, and the solid/liquid ratio r is 0.0667g/mL, the reaction kinetics constant is k = 0.00199 (mol/L) 0.4612/min. Between 20℃ and 80℃, with the increase of temperature, the reaction rate is gradually accelerated, and the reaction changes from chemically controlled to diffusion-controlled. The reaction process is simulated by DFT, and the influence of various factors on the reaction process is deduced. The reaction process and mechanism are determined according to the reaction kinetics and simulation results finally.
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The general application of antibiotics has brought a series of negative impacts on human health and the environment, which has aroused widespread public attention to their removal from aqueous systems. In this study, a chitosan (CS)-linked graphene oxide (GO) composite (GO-CS) was synthesized by a modified Hummers/solvothermal method. It was separated from the mixed aqueous phase by low-speed centrifugation, thereby endowing the GO with high separation efficiency in water. The adsorption of tetracycline (TC), norfloxacin (NOR), and sulfadiazine (SDZ) by GO-CS were then studied by experimental techniques and theoretical calculations. In batch experiments at 298 K and optimal pH, the adsorption capacities of TC, NOR, and SDZ were 597.77, 388.99, and 136.37 mg/g, respectively, which were far better than those for pristine graphene oxide. The spectra results illustrated that the adsorption process was mainly contributed by the interactions between antibiotics and functional groups (carboxyl, hydroxyl, and amino groups) of GO-CS. Furthermore, density functional theory calculations showed that electrostatic interaction and hydrogen bonds are of vital importance for the uptake of the antibiotics; the former is extremely important for TC adsorption. This research will provide theoretical references for the removal of antibiotics by graphene-based composite materials, thus offering their promising application in environmental remediation.
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In (relativistic) electronic structure methods, the quaternion matrix eigenvalue problem and the linear response (Bethe-Salpeter) eigenvalue problem for excitation energies are two frequently encountered structured eigenvalue problems. While the former problem was thoroughly studied, the later problem in its most general form, namely, the complex case without assuming the positive definiteness of the electronic Hessian, is not fully understood. In view of their very similar mathematical structures, we examined these two problems from a unified point of view. We showed that the identification of Lie group structures for their eigenvectors provides a framework to design diagonalization algorithms as well as numerical optimizations techniques on the corresponding manifolds. By using the same reduction algorithm for the quaternion matrix eigenvalue problem, we provided a necessary and sufficient condition to characterize the different scenarios, where the eigenvalues of the original linear response eigenvalue problem are real, purely imaginary, or complex. The result can be viewed as a natural generalization of the well-known condition for the real matrix case.
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The anionic carbonyl complexes of groups IV and V metals are prepared in the gas phase using a laser vaporation-supersonic expansion ion source. The infrared spectra of the TM(CO)<sub>6,7</sub><sup>-</sup> (TM=Ti, Zr, Hf, V, Nb, Ta) anion complexes in the carbonyl stretching frequency region are measured by mass-selected infrared photodissociation spectroscopy. The six-coordinated TM(CO)<sub>6</sub><sup>-</sup> anions are determined to be the coordination saturate complexes for both the group IV and group V metals. The TM(CO)<sub>6</sub><sup>-</sup> complexes of group IV metals (TM=Ti, Zr, Hf) are 17-electron complexes having a <sup>2</sup>A<sub>1g</sub> ground state with D<sub>3d</sub> symmetry, while the TM(CO)<sub>6</sub><sup>-</sup> complexes of group V metals (TM=V, Nb, Ta) are 18-electron species with a closed-shell singlet ground state possessing O<sub>h</sub> symmetry. The energy decomposition analyses indicate that the metal-CO covalent bonding are dominated by TM-(d) → (CO)<sub>6</sub> π-backdonation and TM-(d)←(CO)<sub>6</sub> σ-donation interactions.
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A better understanding of the photophysical processes occurring within organic semiconductors is important for designing and fabricating organic solar cells (OSCs). In this paper, we investigated the triplet‒triplet annihilation process in CuPc thin films with different molecular stacking configurations. The ultrafast transient absorption measurements indicate that the primary annihilation mechanism is one-dimensional exciton diffusion collision destruction. The decay kinetics shows a clearly time-dependent annihilation rate constant with γ ∝ t−1/2. Annihilation rate constants were determined to be γ0 = (2.87 ± 0.02) × 10−20 and (1.42 ± 0.02) × 10−20 cm3·s−1/2 for upright and lying-down configurations, respectively. Compared to the CuPc thin film with an upright configuration, the thin film with a lying-down configuration shows a longer exciton lifetime and a higher absorbance, which are beneficial for OSCs. The results in this paper have important implications on the design and mechanistic understanding of organic optoelectronic devices.

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Vacuum ultraviolet photodissociation dynamics of N2O + hv → N2(X1Σg+) + O(1S0) in the short wavelength tail of D1Σ+ band have been performed using the time-sliced velocity-mapped ion imaging technique by probing the images of the O(1S0) photoproducts at a set of photolysis wavelengths from 121.47 to 123.95 nm. The product total kinetic energy release distributions, vibrational state distributions of the N2(X1Σg+) photofragments and angular anisotropy parameters have been obtained through analyzing the raw O(1S0) images. It is noted that an additional vibrationally excited photoproducts (3≤v≤8) with a Boltzmann-like feature start to appear except for the non-statistical component as the photolysis wavelength decreases to 123.25 nm, and the corresponding populations become more pronounced with decreasing of the photolysis wavelength. Furthermore, the vibrational state specific β-value at each photolysis wavelength exhibits a drastic fluctuation near β=1.75 at v<8, and decreases to a minimum as the vibrational quantum number further increases. While the overall β-value for the N2(X1Σg+) + O(1S0) channel presents a roughly monotonically increasing from the value of 1.63 at 121.47 nm to 1.95 at 123.95 nm. The experimental observations suggest that there is at least one fast nonadiabatic pathway from initially prepared D1Σ+ state to the dissociative state with bent geometry dominating to generate the additional vibrational structures at high photoexcitation energies.
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Catalytic hydrolysis of ammonia borane for dehydrogenation is a promising way for generation and storage of hydrogen energy. Catalysts with reduced utilization of costly noble metals while high activity and stability are highly desired. Herein we show that the catalytic activity of the prototypical Pt/SiO2 catalysts towards ammonia borane hydrolysis could be significantly improved by the presence of a layer of Co(OH)2 beneath the supported Pt nanoparticles. By changing the Pt:Co molar ratio in the Pt-Co(OH)2/SiO2 catalysts, the hydrogen generation rates from ammonia borane hydrolysis show a volcano-type curve, with the maximum catalytic activity at the Pt:Co molar ratio of 1:11. The highest turnover frequency value of 829 molH2·molPt−1·min−1 at room temperature outperforms most of the reported Pt-based catalysts, and the apparent activation energy is drastically decreased to 36.2 kJ/mol from 61.6 kJ/mol for Pt/SiO2. The enhanced catalytic performance of Pt-Co(OH)2/SiO2 is attributed to the electrons donation from Co atoms on Co(OH)2 to Pt occurring at the metal-hydroxide interface, which is beneficial for optimizing the oxidation cleavage of the O−H bond of attacked H2O.

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Herein, we present the decoration of NiFeCoAlOOH nanoparticles onto titanium doped nanoporous hematite (Ti-PH) utilizing a simple electroless ligand-controlled oxidation method for photoelectrochemical water splitting. Owing to the improved oxygen evolution reaction kinetics and reduced charge transfer resistance, the resulting Ti-PH/NiFeCoAlOOH photoanode presents an excellent photocurrent density of 2.46 mA/cm<sup>2</sup> at 1.23V vs. RHE and good stability compared to Ti-PH or bare hematite (H). Furthermore, the onset potential of the photocurrent density is shifted cathodically by ~ 60 mV with reference to the titanium doped nanoporous hematite. This work offers a promising method for designing high-performance, stable, and inexpensive catalysts for photoelectrochemical (PEC) applications.
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Although lead-based halide perovskites have promising applications in optoelectronic devices, these applications are limited by the toxicity of the materials. Therefore, it is necessary to develop lead-free all-inorganic substitute such as tin-based halide perovskites in spite of the enormous challenges in their controllable synthesis and stability. Here, we report the controlled growth of high quality CsSnBr<sub>3</sub> microcrystals on SiO<sub>2</sub>/Si substrates by chemical vapor deposition method. The as-prepared products predominantly show the morphology of triangle star and nail-like rod and the structure of cubic phase. The control of nucleation density and size of CsSnBr<sub>3</sub> microcrystals has been realized by varying the growth temperature. The results of air-exposed samples provide direct evidences for explaining the structural instability of the tin-based perovskites, which is attributed to the production of SnO. The power and temperature dependent photoluminescence spectra reveal that CsSnBr<sub>3</sub> microcrystals with different morphologies possess different exciton binding energies and produce different photoexcitation species due to the quantum confinement effect that changes the electron-hole effect.
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Ultra-wide-bandgap semiconductors have tremendous potential to advance electronic devices, as device performance improves nonlinearly with increasing gap. In this work we employ density-functional theory with the accurate screened-hybrid functional to evaluate the electronic and optical properties of NaYO2 in two different phases. The electronic structure calculation results show that both monoclinic and trigonal phases of NaYO2 exhibit direct bandgaps of 5.6 and 5.4 eV, respectively, offering a physically realistic material platform to derive the semiconductor industry beyond the well-established diamond, and GaN semiconducting materials. Next, we investigate the optical properties and reveal that both phases of NaYO2 are transparent in the infrared and visible regions, thereby, these materials can be used as infrared window materials.
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Polymers are routinely used as embedding matrices for organic molecular phosphors to substantially reduce the non-radiative decay rate and promote room-temperature phosphorescence (RTP). However, most previous studies focus on how glass transition temperature and free volume of various polymers influence RTP efficiency; very little is known on how electronic coupling between the matrix and the phosphor can modulate organic RTP. The current investigation attempts to address the problem by synthesizing a monomeric version of an aromatic ketone phosphor and copolymerizing the ketone with four different types of matrix monomers. The resulting copolymers exhibit clear matrix-dependent RTP efficiency: a gradual decrease of RTP quantum yield from 22% to nearly 0 can be observed when the electronic conjugation of the matrix increases, suggesting that energy dissipation can occur in the triplet excited state via electron exchange when the triplet state of the matrix is close to that of the phosphor. The study provides a guiding principle on regulating the lifetime of triplet-excited states for organic dyes.
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A novel electrochemical non-enzymatic glucose sensor based on three-dimensional Au/MXene nanocomposites was developed. MXenes were prepared using the mild etched method, and the porous foam of Au nanoparticles was combined with the MXene by means of in situ synthesis. By controlling the mass of MXene in the synthesis process, porous foam with Au nanoparticles was obtained. The three-dimensional foam structure of nanoparticles was confirmed by scanning electron microscopy (SEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical performance of the Au/MXene nanocomposites. The Au/MXene nanocomposites acted as a fast redox probe for non-enzymatic glucose oxidation and showed good performance, including a high sensitivity of 22.45 μA mM−1 cm−1 and a wide linear range of 1–12 mM. Studies have shown that MXene as a catalyst-supported material is beneficial to enhance the conductivity of electrons and increase the loading rate of the catalyst materials. The foam structure with Au nanoparticles can provide a larger surface area, increase the contact area with the molecule in the catalytic reaction, and enhance the electrochemical reaction signal. In summary, this study showed that Au/MXene nanoparticles have the potential to be used in non-enzymatic glucose sensors.
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The yolk-shell MIL-125/TiO<sub>2</sub>/Pt/CdS and hollow TiO<sub>2</sub>/Pt/CdS visible-light catalysts were successfully synthesized from MIL-125 by γ-ray irradiation. What is interesting is that during the reduction process by γ-ray irradiation, MOFs are partially or completely hydrolyzed to TiO<sub>2</sub> nanosheets, forming the unique yolk-shell or hollow structure. The hydrogen production rate is 2983.5 μmol·g<sup>-1</sup>·h<sup>-1</sup> for yolk-shell structures and 1934.2 μmol·g<sup>-1</sup>·h<sup>-1</sup> for hollow structures under visible-light illumination, which is 7.9 and 5.1 times higher than that of CdS, respectively. The excellent properties of these photocatalysts may be attributed to the effective absorption and utilization of the light, the porous yolk-shell or hollow structure derived from MIL-125 to facilitate mass transfer, and close contact among CdS nanoparticles, TiO<sub>2</sub> nanosheets and Pt nanoparticles to improve the separation of electron-hole pairs. This research can provide a simple and new method for the construction of high efficiency photocatalysts derived from MOFs using the γ-ray irradiation.
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The electrocatalytic carbon dioxide reduction reaction (CO2RR) producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels. The SnO2 is a good catalyst for CO2-to-HCOOH or CO2-to-CO conversion, with different crystal planes participating the catalytic process. Among them, (110) surface SnO2 is very stable and easy to synthesis. By changing the ratio of Sn:O for SnO2 (110), we have two typical SnO2 thin films: fully oxidized (stoichiometric) and partially reduced. In this work, we are concerned with different metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au)-doped SnO2 (110) of different activity and selectivity for CO2RR. All these changes are manipulated by adjusting the ratio of Sn:O in (110) surface. The results show that stochiometric and reduced Cu/Ag doped SnO2(110) have different selectivity for CO2RR. More specifically, stochiometric Cu/Ag-doped SnO2 (110) tends to generate CO(g). Meanwhile, the reduced surface tends to generate HCOOH(g). Moreover, we also considered the competitive reaction hydrogen evolution reaction(HER). The catalysts SnO2 (110) doped by Ru, Rh, Pd, Os, Ir, and Pt have high activity for HER, and others are good catalysts for CO2RR.
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In this work, we firstly elucidated the ultraviolet light protection dynamics mechanism of the typical hemicyanines of Hemicy and DHemicy by combining the theoretical calculation method and the transient absorption spectra. It was theoretically and experimentally demonstrated that both of Hemicy and DHemicy have strong absorption in UVC, UVB, and UVA regions. Moreover, after absorbing energy, Hemicy and DHemicy can jump into the excited states. Subsequently, the Hemicy and DHemicy will relax to S0 states from S1 states rapidly by the non-adiabatic transition at the conical intersection (CI) point between the potential energy curves of S1 and S0 states and accompany by the trans-cis photoisomerism. The transient absorption spectra showed that the trans-cis photoisomerization will occur within a few picoseconds. Thus, the ultraviolet energy absorbed by Hemicy and DHemicy could be relaxed ultrafast by the non-adiabatic trans-cis photoisomerization processes.
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Specific energy and self-discharge are two important performances of electrochemical capacitors. In this work, we have fabricated the composite electrodes by complexing the negatively charged carboxylated multi-walled carbon nanotubes (cMWCNT) with the redox active units-containing positively charged random copolymers. 2,2,6,6-Tetramethylpiperidinyl-N-oxyl and viologen are employed as model redox active units to exemplify the strategy of the concurrent increase of specific energy and suppression of self-discharge of a two-electrode device. The enhanced specific energy is mainly attributed to the increased electrolyte decomposition window induced by the faster redox reactions than those of the hydrogen and oxygen evolution reactions. The improved performance of self-discharge is due to the suppression of the cross-diffusion and redox shuttling of the redox couples induced by the complexation between the cMWCNT and the copolymers. By employing the redox active units-containing charged copolymers, this work provides a convenient and universal strategy to concurrently increase specific energy and suppress self-discharge of electrochemical capacitors with the carbon-based electrodes.
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It is important to identify non-planar deformations of porphyrin macrocycle in metallo-porphyrin proteins due to their functional relevance. The relationship between non-planar deformations of porphyrin macrocycle and low frequency Raman spectral bands of Ni(II) Meso-tetraphenyl porphyrin (NiTPP), with different coordination numbers , was studied by density functional theory (DFT) , normal coordinate structural decomposition (NSD) method and Raman experiments. The results show that the crystal of four-coordinate NiTPP has two major kinds of nonplanar deformations: ruffling and saddling. The non-planar deformations of ruffling and saddling for NiTPP are 1.473 Å and 0.493 Å determined by DFT calculation. The ruffling and saddling deformations can be identified by using the low frequency Raman characteristic peaks (r12 ,r13 ) and (r16 ,r17 ), respectively. When four-coordinate NiTPP is transformed to the six-coordinate bis(pyrrolidine) NiTPP (NiTPP(Pyr)2), the large non-planar distortion of the porphyrin macrocycle almost disappears, with the non-planar deformation of saddling only about 0.213 Å estimated by DFT calculation. Experimentally, we can make use of the characteristic peaks of low frequency Raman spectra to identify the saddling deformation beyond 0.25 Å.
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Though poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been widely adopted as hole transport material (HTM) in flexible perovskite solar cells (PSCs), arising from high optical transparency, good mechanical flexibility, and high thermal stability, its acidity and hygroscopicity would inevitably hamper the long-term stability of the PSCs and its energy level does not match well with that of perovskite materials which would lead to a relatively low open-circuit voltage (VOC). In this investigation, p-type delafossite CuCrO2 nanoparticles synthesized through hydrothermal method have been employed as an alternative HTM for triple cation perovskite [(FAPbI3)0.87(MAPbBr3)0.13]0.92[CsPbI3]0.08 (possessing better photovoltaic performance and stability than conventional CH3NH3PbI3) based inverted architecture PSCs. The average VOC of PSCs has increased from 908 mV of the devices with PEDOT:PSS HTM to 1020 mV of the devices with CuCrO2 HTM. Ultraviolet photoemission spectroscopy measurement demonstrates the energy band alignment between CuCrO2 and perovskite is better than that between PEDOT:PSS and perovskite, the electrochemical impedance spectroscopy indicates CuCrO2 based PSCs exhibit larger recombination resistance and longer charge carrier lifetime, which contribute to the high VOC of CuCrO2 HTM based PSCs.
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The burgeoning two-dimensional (2D) layered materials provide a powerful strategy to realize efficient light-emitting devices. Among them, Gallium telluride (GaTe) nanoflakes, emerging strong photoluminescence (PL) emission from multilayer to bulk crystal, relax the stringent fabrication requirements of nanodevices. However, detailed knowledge on the optical properties of GaTe varied as layer thickness is still missing. Here we perform thickness-dependent PL and Raman spectra, as well as temperature-dependent PL spectra of GaTe nanoflakes. Spectral analysis reveals a spectroscopic signature for the coexistence of both the monoclinic and hexagonal phases in GaTe nanoflakes. To understand the experimental results, we propose a crystal structure where the hexagonal phase is on the top and bottom of nanoflakes while the monoclinic phase is in the middle of the nanoflakes. On the basis of temperature-dependent PL spectra, the optical gap of the hexagonal phase is determined to 1.849 eV, which can only survive under a temperature higher than 200 K with the increasing phonon population. Furthermore, the exciton-phonon interaction of the hexagonal phase is estimated to be 1.24 meV/K. Our results prove the coexistence of dual crystalline phases in multilayer GaTe nanoflakes, which may provoke further exploration of phase transformation in GaTe materials, as well as new applications in 2D light-emitting diodes and heterostructure-based optoelectronics.
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We report a measurement of electron momentum distributions of valence orbitals of cyclopentene employing symmetric noncoplanar (e, 2e) kinematics at impact energies of 1200 and 1600 eV plus the binding energy. Experimental momentum profiles for individual ionization bands are obtained and compared with theoretical calculations considering nuclear dynamics by harmonic analytical quantum mechanical and thermal sampling molecular dynamics approaches. The results demonstrate that molecular vibrational motions including ring-puckering of this flexible cyclic molecule have obvious influences on the electron momentum profiles for the outer valence orbitals, especially in the low momentum region. For π*-like molecular orbitals 3a'' and 2a''+3a' , the impact-energy dependence of the experimental momentum profiles indicates a distorted wave effect.
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Red phosphorus (RP) has attracted more attention as a promising sodium storage material due to its ultra-high theoretical capacity, suitable sodiation potential. However, the low intrinsic electrical conductivity and large volume change of pristine RP lead to high polarization and fast capacity fading during cycling. Herein, surface synergistic protections on red phosphorus composite is successfully proposed by conductive poly (3, 4-ethylenedioxythiophene) (PEDOT) coating and electrolyte strategy. Nanoscale RP is confined in porous carbon skeleton and the outside is packaged by PEDOT coating via in-situ polymerization. Porous carbon provides rich access pathways for rapid Na+ diffusion and empty spaces accommodate the volume expansion of RP; PEDOT coating isolates the direct contact between electrolyte and active materials to form a stable solid electrolyte interphase. In addition, the reformulated electrolyte with 3 wt% SbF3 additive can stabilize the electrode surface and thus enhance the electrochemical performance, especially cycling stability and rate capability (433 mAh g-1 at high current density of 10 A g-1).
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Metal-halide perovskite solar cells (PSCs) have attracted considerable attention during the past decade. However, due to the existence of non-radiative recombination losses, the best power conversion efficiency (PCE) is still lower than the theoretical limit defined by shockley-Queser theory. In this work, we investigate1,2,3-oxathiazin-4(3h)-one,6-methyl-2,2-dioxide (Acesulfame Potassium, abbreviated as AK) as a additional dopant for the 2,2′,7,7′-Tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (Spiro-OMeTAD) and fabricate PSCs in the air. It is found that 12 mol % fraction of AK relative to lithium bis((trifluoromethyl)sulfonyl)-amide (Li-TFSI) reduced the non-radiative recombination from 86.05 % to 69.23 %, resulting in an average 0.08 V enhancement of Voc. The champion solar cell gives a PCE up to 21.9% and over 84% retention of the initial value during 720 h aging in dry air with 20%~30% humidity.
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We have investigated the adsorption of 9 different adatoms on the (111) and (100) surfaces of Iridium (Ir) using first principles density functional theory. The study explores surface functionalization of Ir which would provide important information for further study towards investigating its functionality in catalysis and other surface applications. The adsorption energy, stable geometry, density of states and magnetic moment are the physical quantities of our interest. Strong hybridization between the adsorbates and the substrate electronic states revealed to impact the adsorption, while the magnetic moment of the adsorbates found to be suppressed. In general, stronger binding is observed on the (100) surface.
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Based on density functional theory (DFT), a new silicon allotrope (C2-Si) is proposed in this work. The mechanical stability and dynamic stability of C2-Si are examined based on the elastic constants and phonon spectrum. According to the BH/GH values, C2-Si has ductility under ambient pressure; compared with Si64, Si96, I4/mmm and h-Si6, C2-Si is less brittle. Within the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional, C2-Si is an indirect narrow band gap semiconductor, and the band gap of C2-Si is only 0.716 eV, which is approximately two-thirds that of c-Si. The ratios of the maximum and minimum values of the Young's modulus, shear modulus and Poisson's ratio in their 3D spatial distributions for C2-Si are determined to characterize the anisotropy. In addition, the anisotropy in different crystal planes is also investigated via 2D representations of the Young’s modulus, shear modulus and Poisson’s ratio. In addition, among more than ten silicon allotropes, C2-Si has the strongest absorption ability for visible light.
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The aggregation of Perylene Diimide (PDI) and its derivatives strongly depends on the molecular structure and therefore has a great impact on the excited states. By regulating the molecular stacking such as monomer, dimer, J- and/or H-aggregate, the formation of different excited states is adjustable and controllable. In this study, we have synthesized two kinds of PDI derivatives - undecane-substituted PDI (PDI-1) and diisopropylphenyl-substituted PDI (PDI-2), and the films are fabricated with spin-coating method. By employing photoluminescence (PL), time-resolved photoluminescence (TRPL), and transient absorption (TA) spectroscopy, the excited-state dynamics of two PDI amorphous films have been investigated systematically. The result reveals that both films have formed excimer after photoexcitation mainly due to the stronger electronic coupling among molecule aggregate in the amorphous film. It should be noted that the excited state dynamics in PDI-2 show a singlet fission like process, which is evidenced by the appearance of triplet state absorption. This study provides the dynamics of excited state in amorphous PDI films, and pave the way for better understanding and adjusting the excited state of amorphous films.
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In order to reduce the impact of CdS photogenerated electron-hole recombination on its photocatalytic performance, a narrow band gap semiconductor MoS2 and organic macromolecular cucurbit[n]urils(Q[n]) were used to modify CdS. Q[n]/CdS-MoS2 (n=6, 7, 8) composite photocatalysts were synthesized by hydrothermal method. Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (SEM), ultraviolet-visible (UV-Vis) and photoluminescence spectrum (PL) were used to characterize the structure, morphology and optical properties of the products, and the catalytic degradation of the solutions of methylene blue, rhodamine B and crystal violet by Q[n]/CdS-MoS2 composite catalyst was investigated. The results showed that the Q[n] played a regulatory role on the growth and crystallization of CdS-MoS2 particles, Q[n]/CdS-MoS2 (n=6, 7, 8) formed flower clusters with petal-like leaves, the flower clusters of petal-like leaves increased the surface area and active sites of the catalyst, the Q[n]/CdS-MoS2 barrier width decreased, the electron-hole pair separation efficiency was improved in the Q[6]/Cds-MoS2. Q[n] makes the electron-hole pair to obtain better separation and migration. The Q[6]/CdS-MoS2 and Q[7]/CdS-MoS2 have good photocatalytic activity for methylene blue, and the catalytic process is based on hydroxyl radical principle.
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The laser-induced ﬂuorescence excitation spectra of UF have been recorded in the range of 17000−19000 cm-1 using two-dimensional spectroscopy. High resolution dispersed ﬂuorescence spectra and fluorescence decay curves time-resolved fluorescence spectroscopy were also recorded. Three rotationally resolved bands have been intensively analyzed, and all bands were found to be derived from the ground state X(1)4.5 with a rotational constant of 0.23421 cm-1. The low-lying electronic states have been observed near 435 and 651 cm-1 in the dispersed fluorescence spectra, which were assigned as Ωʹ = 3.5, and 2.5, respectively. The vibrational constants for the X(1)4.5 and X(1)3.5 states have been calculated. The branching ratios of the dispersed fluorescence spectra for the [18.62]3.5, [17.72]4.5, and [17.65]4.5 states were reported. Radiative lifetimes of 332(9), 825(49), and 433(15) ns for the [18.62]3.5, [17.72]4.5, and [17.65]4.5 states were obtained by fitting the fluorescence decay curves time-resolved fluorescence spectroscopy, respectively. Transition dipole moments were performed using the branching ratios and the radiative lifetimes.
Dimension-controllable supramolecular organic frameworks (SOFs) with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of CB[8] and coumarin-modified tetraphenylethylene derivatives (TPEC). The three-dimensional (3D) layered SOFs could be constructed from the gradual stacking of two-dimensional (2D) mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration. Upon light irradiation under the wavelength of 350 nm, the photodimerization of coumarin moieties occurred, which resulted in the transformation of the resultant TPECn/CB[8]4n 2D SOFs into robust covalently-connected 2D polymers with molecular thickness. Interestingly, the supramolecular system of TPECn/CB[8]4n exhibited intriguing multicolor fluorescence emission from yellow to blue from 0 to 24 hours at 365 nm irradiation, possessing potential applicability for cell imaging and photochromic fluorescence ink.
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Owing to their unique structural, electronic, and physico-chemical properties, molybdenum clusters are expected to play an important role in future nanotechnologies. However, their ground states are still under debate. In this study, the crystal structure analysis by particle swarm optimization (CALYPSO) approach is used for the global minima search, which is followed by first-principles calculations, to detect an obvious dimerization tendency in Mo<sub>n</sub> (n = 2-18) clusters when the 4<i>s</i> and 4<i>p</i> semicore states (SCS) are not regarded as the valence states. Further, the clusters with even number of atoms are usually magic clusters with high stability. However, after including the 4<i>s</i> and 4<i>p</i> electrons as valence electrons, the dimerization tendency exhibits a drastic reduction because the average hybridization indices H<sub>sp</sub>, H<sub>sd</sub>, and H<sub>pd</sub> are reduced significantly. Overall, this work reports new ground states of Mo<sub>n</sub> (n = 11, 14, 15) clusters and proves that SCS are essential for Mo<sub>n</sub> clusters.
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Rational designs of electrocatalytic active sites and architectures are of great importance to develop cost-efficient non-noble metal electrocatalysts towards efficient oxygen reduction reaction (ORR) for high-performance energy conversion and storage devices. In this paper, active amorphous Fe-based nanoclusters (Fe NC) are elaborately embedded at the inner surface of balloon-like N-doped hollow carbon (Fe NC/C<sub>h</sub> sphere) as an efficient ORR electrocatalyst with an ultrathin wall of about 10 nm. When evaluated for electrochemical performance, Fe NC/C<sub>h</sub> sphere exhibits decent ORR activity with a diffusion-limited current density of ~5.0 mA cm<sup>-2</sup> and a half-wave potential of ~0.81 V in alkaline solution, which is comparable with commercial Pt/C and superior to Fe nanoparticles (NP) supported on carbon sheet (Fe NP/C sheet) counterpart. The electrochemical analyses combined with electronic structure characterizations reveal that robust Fe-N interactions in amorphous Fe nanoclusters are helpful for the adsorption of surface oxygen-relative species, and the strong support effect of N-doped hollow carbon is benefit for accelerating the interfacial electron transfer, which jointly contributes to improved ORR kinetics for Fe NC/C<sub>h</sub> sphere.
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In order to search for high energy density materials, various 4, 8-dihydrodifurazano[3,4-b,e]pyrazine based energetic materials were designed. Density functional theory was employed to investigate the relationships between the structures and properties. The calculated results indicated that the properties of these designed compounds were influenced by the energetic groups and heterocyclic substituents. The –N3 energetic group was found to be the most effective substituent to improve the heats of formation of the designed compounds while the tetrazole ring/–C(NO2)3 group contribute much to the values of detonation properties. The analysis of bond orders and bond dissociation energies showed that the addition of –NHNH2, –NHNO2, –CH(NO2)3 and –C(NO2)3 groups will decrease the bond dissociation energies remarkably. Compounds A8, B8, C8, D8, E8, and F8 were finally screened as the potential candidates for high energy density materials since these compounds possess excellent detonation properties and acceptable thermal stabilities. Additionally, the electronic structures of the screened compounds were calculated.
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After binding to human serum albumin (HSA), bilirubin could undergo photo-isomerization and photo-induced cyclization process. The latter process would result the formation of a product named lumirubin. These photo induced behaviors are the fundamental of clinical therapy for neonatal jaundice. Previous studies have reported that the addition of long chain fatty acids is beneficial to the generation of lumirubin, yet no kinetic study have revealed the mechanism behind. In this study, how palmitic acid affects the photochemical reaction process of bilirubin in HSA is studied by using femtosecond transient absorption and fluorescence up-conversion techniques. With the addition of palmitic acid, the excited population of bilirubin prefers to return to its hot ground state (S0) through a 4 picosecond decay channel rather than the intrinsic ultrafast decay pathways (<1 picosecond). This effect prompts the Z-Z to E-Z isomerization at the S0 state and then further increase the production yield of lumirubin. This is the first time to characterization the promoting effect of long chain fatty acid in the process of phototherapy with femtosecond time resolution spectroscopy and the results can provide useful information to benefit the relevant clinical study.
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The photochemical reaction of potassium ferrocyanide (K4Fe(CN)6}) exhibits excitation wavelength dependence and non-Kasha rule behavior. In this study, the excited-state dynamics of K4Fe(CN)6 were studied by transient absorption spectroscopy. Excited state electron detachment (ESED) and phtoaquation reactions were clarified by comparing the results of 260 , 320 , 340 , and 350 nm excitations. ESED is the path to generate a hydrated electron (eaq-). ESED energy barrier varies with the excited state, and it occurrs even at the first singlet excited state (1T1g). The 1T1g state shows ~0.2 ps lifetime and converts into triplet [Fe(CN)6]4- by intersystem crossing. Subsequently, 3[Fe(CN)5]3- appears after one CN- ligand is ejected. In sequence, H2O attacks [Fe(CN)5]3- to generate [Fe(CN)5H2O]3- with a time constant of approximately 20 ps. The 1T1g state and eaq- exhibit strong reducing power. The addition of UMP to the K4Fe(CN)6 solution decreased the yield of eaq- and reduced the lifetimes of the eaq- and 1T1g state. The obtained reaction rate constant of 1T1g state and UMP was 1.7×1014 M-1 s-1, and the eaq- attachment to UMP was ~8×109 M-1 s-1. Our results indicate that the reductive damage of K4Fe(CN)6 solution to nucleic acids under ultraviolet irradiation cannot be neglected.
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Rhodium-catalyzed cycloaddition reaction was calculated by density functional theory (DFT) M06-2X method to directly synthesize benzoxepine and coumarin derivatives. In this paper, we conducted a computational study of two competitive mechanisms in which the carbon atom of acetylene or carbon monoxide attacked and inserted from two different directions of the six-membered ring reactant to clarify the principle characteristics of this transformation. The calculation result reveal (1) the insertion process of alkyne or carbon monoxide is the key step of the reaction; (2) For the (5 + 2) cycloaddition reaction of acetylene, higher energy is required to break the Rh-O bond of the reactant, and the reaction tends to complete the insertion from the side of the Rh-C bond; (3) For the (5 + 1) cycloaddition of carbon monoxide, both reaction paths have lower activation free energy, and the two will generate a competition mechanism.
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Consistency between density functional theory calculations and X-ray photoelectron spectroscopy measurements confirms our predications on the undercoordination-induced local bond relaxation and core level shift of alkali metal, which determine the surface, size and thermal properties of materials. Zone-resolved photoelectron spectroscopy analysis method and bond order-length-strength theory can be utilized to quantify the physical parameters regarding bonding identities and electronic property of metal surfaces, which allows for the study of the core-electron binding-energy shifts in alkali metals. By employing these methods and first principle calculation in this work, we can obtain the information of bond and atomic cohesive energy of under-coordinated atoms at the alkali metal surface. In addition, the effect of size and temperature towards the binding-energy in the surface region can be seen from the view point of Hamiltonian perturbation by atomic relaxation with atomic bonding.
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Methyl 2-furoate (FAME2) is a renewable biofuel with the development of the new synthesis method of dimethyl furan-2,5-dicarboxylate. The potential energy surfaces (PES) of H-abstractions and OH-additions between FAME2 and hydroxyl radical (OH) were studied at the CCSD(T)/CBS//M062X/cc-pVTZ level. The following isomerization and decomposition reactions were also determined for the main radicals produced. The results show that the H-abstraction on the branch methyl group is the dominant channel and that the OH-addition reactions on the furan ring has a significant pressure dependency. The current rate coefficients provide important kinetic data for the further improving of the combustion mechanism of FAME2, which bring a trusty reference for further research on practical fuels.
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The vacuum ultraviolet (VUV) photodissociation of OCS via the F 31Π Rydberg states was investigated in the range of 134–140 nm, by means of the time-sliced velocity map ion imaging technique. The images of S (1D2) products from the CO (X1Σ+) + S (1D2) dissociation channel were acquired at five photolysis wavelengths, corresponding to a series of symmetric stretching vibrational excitations in OCS (F 31Π, v1=0-4). The total translational energy distributions, vibrational populations and angular distributions of CO (X1Σ+, v) coproducts were derived. The analysis of experimental results suggests that the excited OCS molecules dissociate to CO (X1Σ+) and S (1D2) products via non-adiabatic couplings between the upper F 31Π states and the lower-lying states both in the C∞v and Cs symmetry. Furthermore, strong wavelength dependent behavior has been observed: the greatly distinct vibrational populations and angular distributions of CO (X1Σ+, v) products from the lower (v1=0-2) and higher (v1=3,4) vibrational states of the excited OCS (F 31Π, v1) demonstrate that very different mechanisms are involved in the dissociation processes. This study provides evidence for the possible contribution of vibronic coupling and the crucial role of vibronic coupling on the VUV photodissociation dynamics.

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The hierarchical stochastic Schrödinger equations (HSSE) are a kind of numerically exact wavefunction-based approaches suitable for the quantum dynamics simulations in a relatively large system coupled to a bosonic bath. Starting from the influence-functional description of open quantum systems, this review outlines the general theoretical framework of HSSEs and their concrete forms in different situations. The applicability and efficiency of HSSEs are exemplified by the simulations of ultrafast excitation energy transfer processes in large-scale systems.
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Stars with masses between 1 and 8 solar masses (M⊙) lose large amounts of material in the form of gas and dust in the late stages of stellar evolution, during their Asymptotic Giant Branch phase. Such stars supply up to 35% of the dust in the interstellar medium and thus contribute to the material out of which our solar system formed. In addition, the circumstellar envelopes of these stars are sites of complex, organic chemistry with over 80 molecules detected in them. We show that internal ultraviolet photons, either emitted by the star itself or from a close-in, orbiting companion, can significantly alter the chemistry that occurs in the envelopes particularly if the envelope is clumpy in nature. At least for the cases explored here, we find that the presence of a stellar companion, such as a white dwarf star, the high flux of UV photons destroys H2O in the inner regions of carbon-rich AGB stars to levels below those observed and produces species such as C+ deep in the envelope in contrast to the expectations of traditional descriptions of circumstellar chemistry.
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Two-photon fluorescence dyes have shown promising applications in biomedical imaging. However, the substitution site effect on geometric structures and photophysical properties of fluorescence dyes is rarely illustrated in detail. In this work, a series of new lipid droplets detection dyes are designed and studied, molecular optical properties and non-radiative transitions are analyzed. The intramolecular weak interaction and electron-hole analysis reveal its inner mechanisms. All dyes are proved to possess excellent photophysical properties with high fluorescence quantum efficiency and large stokes shift as well as remarkable TPA cross section. Our work reasonably elucidates the experimental measurements and the effects of substitution site on two-photon absorption and excited states properties of Lipid droplets detection NAPBr dyes are highlighted, which could provide a theoretical perspective for designing efficient organic dyes for lipid droplets detection in biology and medicine fields.
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We predict two novel group 14 element alloys Si2Ge and SiGe2 in P6222 phase in this work through first-principles calculations. The structures, stability, elastic anisotropy, electronic and thermodynamic properties of these two proposed alloys are investigated systematically. The proposed P6222-Si2Ge and -SiGe2 have a hexagonal symmetry structure, and the phonon dispersion spectra and elastic constants indicate that these two alloys are dynamically and mechanically stable at ambient pressure. The elastic anisotropy properties of P6222-Si2Ge and -SiGe2 are examined elaborately by illustrating the surface constructions of Young’s modulus, the contour surfaces of shear modulus, and the directional dependences of Poisson’s ratio, as well as discussing and comparing the differences with their corresponding group 14 element allotropes P6222-Si3 and -Ge3. Moreover, the Debye temperature and sound velocities are analyzed to study the thermodynamic properties of the proposed P6222-Si2Ge and -SiGe2.
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Herein we present a facile approach for the preparation of a novel hierarchically porous carbon, in which seaweeds serve as carbon source and KOH as activator. The fabricated KOH-activated seaweed carbon (K-SC) displays strong affinity towards tetracycline (TC) with maximum uptake quantity of 853.3 mg g–1, significantly higher than other TC adsorbents. The superior adsorption capacity ascribes to large specific surface area (2614 m2 g−1) and hierarchically porous structure of K-SC, along with strong π–π interactions between TC and K-SC. In addition, the as-prepared K-SC exhibits fast adsorption kinetics, capable of removing 99% of TC in 30 min. Meanwhile, the exhausted K-SC can be regenerated for four cycling adsorption without an obvious degradation in capacities. More importantly, pH and ionic strengths barely affect the adsorption performance of K-SC, implying electrostatic interactions hardly play any role in TC adsorption process. Furthermore, the K-SC packed fixed-bed column (0.1 g of adsorbents) can continually treat 2780 mL solution spiked with 5.0 mg g–1 TC before reaching the breakthrough point. All in all, the fabricated K-SC equips with high adsorption capacity, fast adsorption rate, glorious anti-interference capability and good reusability, which make it holding great feasibilities for treating TC contamination in real applications.
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Theoretical study was carried out with OX2 (X = Halogen) molecules and calculation results showed that delocalized π36 bonds exists in their electronic structures and O atoms adopt the sp2 type of hybridization, which violated the VSEPR theory’s prediction of sp3 type. Delocalization stabilization energy (DSE) was proposed to measure delocalized π36 bond’s contribution to energy decrease and proved that it brings extra-stability to the molecule. According to our analyses, these phenomena can be summarized as a kind of coordinating effect.

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The boom in ultra-thin electronic devices and the growing need for humanization greatly facilitated the development of wearable flexible micro-devices. But the technology to deposit electrode material on flexible substrate is still in its infancy. Herein, the flexible symmetric micro-supercapacitors made of carbon nanotubes (CNTs) on commercial printing paper as electrode materials were fabricated by combining tetrahedral preparator auxiliary coating method and laser-cutting interdigital configuration technique on a large scale. The electrochemical performance of obtained micro-supercapacitors can be controlled and tuned by simple choosing the different model of tetrahedral preparatory to obtain CNTs film of different thickness. As expected, the micro-supercapacitor based on CNTs film can deliver an areal capacitance of up to 4.56 mF cm-2 at current of 0.02 mA. Even if, micro-supercapacitor undergo continuous 10000 cycles, the performance of device can still remain nearly 100%. The as-demonstrated tetrahedral preparator auxiliary coating method and laser-cutting interdigital configuration technique provide new perspective for preparing microelectronics in an economical way. The paper electrode appended by CNTs achieves steerable areal capacitance, showing broad application prospect in fabricating asymmetric micro-supercapacitor with flexible planar configurations in the future.
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Smart functional microgels hold great potential in a variety of applications, especially in drug transportation. However, current drug carriers based on physiological internal stimuli cannot efficiently orientate to designated locations. Therefore, it is necessary to introduce the self-propelled particles to the drug release of the microgels. In order to study self-propulsion of microgels induced by light, it is also a challenge to prepare micron-sized microgels so that they can be observed directly under optical microscopes. This paper presents a method to prepare phototactic microgels with photoresponsive properties. The microgel particles is observed by confocal laser scanning microscopy (CLSM). The photoresponsive properties of microgels are fully investigated by various instruments. Light can also regulate the state of the microgel solution, making it switch between turbidity and clarity. The phototaxis of particles irradiated by UV light was studied, which may be used for microgels enrichment and drug transportation and release.
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In this study, the application of bovine serum albumin (BSA) to glucose- sensitive materials was proposed for the first time. Au-CuO bimetallic nanoclusters (Au-CuO/BSA) were prepared using BSA as a template, the new sensing material (Au-CuO/BSA/MWCNTs) was synthesized by mixing with multi-walled carbon nanotubes (MWCNT) and applied to non-enzymatic electrochemical sensors to detect glucose stably and effectively under neutral conditions. The scanning electron microscopy was used to investigate the morphology of the synthesized nanocomposite. The electrochemical properties of the sensor were studied by cyclic voltammetry. Glucose detection experiments showed that Au-CuO/BSA/MWCNTs/Au electrode had good glucose detection ability, stability, accuracy, repeatability, and high selectivity in neutral environment. Unlike existing glucose-sensitive materials, due to the use of BSA, the composite material is firmly fixed to the electrode surface without a Nafion solution, which reduces the current blocking effect on the modified electrode. The composite materials can be effectively preserved for extremely long periods, higher than 80% activity was maintained at room temperature in a closed environment for 3 to 4 months, due to the special effects of BSA. In addition, the feasibility of using BSA in glucose-sensitive materials was confirmed.
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Our experimental progresses on the reaction dynamics of dissociative electron attachment (DEA) to carbon dioxide (CO2) are summarized in this review. First, we introduce some fundamentals about the DEA dynamics and provide an epitome about the DEAs to CO2. Second, our development on the experimental techniques is described, in particular, on the high-resolution velocity map imaging apparatus in which we put a lot of efforts during the past two years. Third, our findings about the DEA dynamics of CO2 are surveyed and briefly compared with the others’ work. At last, we give a perspective about the applications of the DEA studies and highlight the inspirations in the production of molecular oxygen on Mars and the catalytic transformations of CO2.
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Si (111) electrode has been widely used in electrochemical and photoelectrochemical studies. The potential dependent measurements of the second harmonic generation (SHG) were performed to study Si (111) electrolyte interface. At diﬀerent azimuthal angles of the Si (111) and under diﬀerent polarization combinations, the curve of the intensity of SHG with extern potential have different form of line or parabola. A quantitative analysis showed that this differences of the potential-dependence can be explained by the isotropic and anisotropic contribution of the Si (111) electrode. The change in isotropic and anisotropic contribution of the Si (111) electrode may be attributed to the increase in doping concentration of Si (111) electrodes.
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Reactions of gas-phase species with small molecules are being actively studied to understand the elementary steps and mechanistic details of related condensed-phase processes. Activation of the very inert N≡N triple bond of dinitrogen molecule by isolated gas-phase species has attracted considerable interest in the past few decades. Apart from molecular adsorption and dissociative adsorption, interesting processes such as C–N coupling and degenerate ligand exchange were discovered. The present review article focuses on the recent progress on adsorption, activation, and functionalization of N2 by gas-phase species (particularly metal cluster ions) using mass spectrometry, infrared photo-dissociation spectroscopy, anion photoelectron spectroscopy, and quantum chemical calculations including density functional theory and high-level ab-initio calculations. Recent advances including characterization of adsorption products, dependence of clusters' reactivity on their sizes and structures, and mechanisms of N≡N weakening and splitting have been emphasized and prospects have been discussed.
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Defect-mediated processes in two-dimensional transition metal dichalcogenides have a significant influence on their carrier dynamics and transport properties, however, the detailed mechanisms remain poorly understood. Here, we present a comprehensive ultrafast study on defect-mediated carrier dynamics in ion exchange prepared few-layer MoS<sub>2</sub> by femtosecond time-resolved Vis-NIR-MIR spectroscopy. The broadband photobleaching feature observed in the near-infrared transient spectrum discloses that the mid-gap defect states are widely distributed in few-layer MoS<sub>2</sub> nanosheets. The processes of fast trapping of carriers by defect states and the following nonradiative recombination of trapped carriers are clearly revealed, demonstrating the mid-gap defect states play a significant role in the photoinduced carrier dynamics. The positive to negative crossover of the signal observed in the mid-infrared transient spectrum further uncovers some occupied shallow defect states distributed at less than 0.24 eV below the conduction band minimum. These defect states can act as effective carrier trap centers to assist the nonradiative recombination of photo-induced carriers in few-layer MoS<sub>2</sub> on the picosecond time scale.
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Silicon bulk etching is an important part of micro-electro-mechanical system (MEMS) technology. In this work, a novel etching method is proposed based on the vapor from TMAH solution heated up to boiling point. The monocrystalline silicon wafer is positioned over the solution surface and can be anisotropically etched by the produced vapor. This etching method does not rely on the expensive vacuum equipment used in dry etching. Meanwhile, it presents several advantages like low roughness, high etching rate and high uniformity compared with the conventional wet etching methods. The etching rate and roughness can reach 2.13 μm/min and 1.02 nm, respectively. To our knowledge, this rate is the highest record for the wet etching based on TMAH. Furthermore, the diaphragm structure and Al-based pattern on the non-etched side of wafer can maintain intact without any damage during the back-cavity fabrication. Finally, an etching mechanism has been proposed to illustrate the observed experimental phenomenon. It is suggested that there is a water thin film on the etched surface during the solution evaporation. It is in this water layer that the ionization and etching reaction of TMAH proceed, facilitating the desorption of hydrogen bubble and the enhancement of molecular exchange rate.
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Methyl vinyl ketone oxide (MVCI), an unsaturated four-carbon Criegee intermediate produced from the ozonolysis of isoprene has been recognized to play a key role in determining the tropospheric OH concentration. It exists in four configurations (anti_anti, anti_syn, syn_anti and syn_syn) due to two different substituents of saturated methyl and unsaturated vinyl groups. In this study, we have carried out the electronic structure calculation at the multi-configurational CASSCF and multi-state MS-CASPT2 levels, as well as the trajectory surface-hopping (TSH) nonadiabatic dynamics simulation at the CASSCF level to reveal the different fates of syn/anti configurations in photochemical process. Our results show that the dominant channel for the S1-state decay is a ring closure, isomerization to dioxirane, during which, the syn(C-O) configurations with an intramolecular hydrogen bond show slower nonadiabatic photoisomerization. More importantly, it has been found for the first time in photochemistry of Criegee intermediate that the cooperation of two heavy groups (methyl and vinyl) leads to an evident pyramidalization of C3 atom in MVCI, which then results in two structurally-independent minimal-energy crossing points (CIs) towards the syn(C-O) and anti(C-O) sides, respectively. The preference of surface hopping for a certain CI is responsible for the different dynamics of each configuration.
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The photodissociation dynamics of AlO at 193 nm is studied using time-sliced ion velocity mapping. Two dissociation channels are found through the speed and angular distributions of aluminum ions: one is one photon dissociation of the neutral AlO to generate Al(2Pu) + O(3Pg), and the other is two-photon ionization and then dissociation of AlO+ to generate Al+(1Sg) + O(3Pg). Each dissociation channel includes the contribution of AlO in the vibrational states v = 0-2. The anisotropy parameter of the neutral dissociation channel is more dependent on the vibration state of AlO than the ion dissociation channel.
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We report a study on photo-ionization of benzene and aniline with incidental subsequent dissociation by the customized reflection time-of-flight mass spectrometer utilizing a deep ultraviolet (DUV) 177.3 nm laser. Highly efficient ionization of benzene is observed with a weak C4H3+ fragment formed by undergoing disproportional C−C bond dissociation. In comparison, a major C5H6+• fragment and a minor C6H6+• radical are produced in the DUV ionization of aniline pertaining to the removal of CNH* and NH* radicals, respectively. First-principles calculation is employed to reveal the photo-dissociation pathways of these two molecules having a structural difference of just an amino group. It is demonstrated that hydrogen atom transfer (HAT) plays an important role in the cleavage of C−C or C−N bonds in benzene and aniline ions. This study helps understand the underlying mechanisms of chemical bond fracture of benzene ring and related aromatic molecules.
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Recent experiments report the rotation of FA (FA= HC[NH2]2+) cations significantly influence the excited-state lifetime of FAPbI3. However, the underlying mechanism remains unclear. Using ab initio nonadiabatic (NA) molecular dynamics combined with time-domain density functional simulations, we have demonstrated that eeorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions. Slow nuclear motions simultaneously increase the decoherence time but which is overcomed by the reduced NA coupling, extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3, which occurs within sub-nanosecond and agrees with experiment. Our study established the mechanism for the experimentally reported prolonged excited-state lifetime, providing rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.
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Sum frequency generation vibrational spectroscopy (SFG-VS) is a powerful technique for determining molecular structures at both buried interface and air surface. Distinguishing the contribution of SFG signals from buried interface and air surface is crucial to the applications in devices such as microelectronics and bio-tips. Here we demonstrate that the SFG spectra from buried interface and air surface can be differentiated by controlling the film thickness and employment of surface-plasmon enhancement. Using substrate-supported PMMA films as a model, we have visualized the variations in the contribution of SFG signals from buried interface and air surface. By monitoring carbonyl and C-H stretching groups, we found that SFG signals are dominated by the moieties (-CH2, -CH3, -OCH3 and C=O) segregated at the PMMA/air surface for the thin films while they are mainly contributed by the groups (-OCH3 and C=O) at the substrate/PMMA buried interface for the thick films. At the buried interface, the tilt angle of C=O decreases from 65° to 43° as the film preparation concentration increases; in contrast, the angles at the air surface fall in the range between 38° and 21°. Surface plasmon generated by gold nanorod can largely enhance SFG signals, particularly the signals from the buried interface.
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Inspired by the branching corrected surface hopping (BCSH) method [J. Xu and L. Wang, J. Chem. Phys. 150, 164101 (2019)], we present two new decoherence time formulas for trajectory surface hopping. Both the proposed linear and exponential formulas characterize the decoherence time as functions of the energy difference between adiabatic states and correctly capture the decoherence effect due to wave packet reflection as predicted by BCSH. The relevant parameters are trained in a series of 200 diverse models with different initial nuclear momenta and the exact quantum solutions are utilized as references. As demonstrated in the three standard Tully models, the two new approaches exhibit significantly higher reliability than the widely used counterpart algorithm while holding the appealing efficiency, thus promising for nonadiabatic dynamics simulations of general systems.
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A fundamental study on C?C coupling that is the crucial step in the Fischer-Tropsch synthesis (FTS) process to obtain multi-carbon products is of great importance to tailor catalysts and then guide a more promising pathway. It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process, while the related mechanism is elusive. Herein, the reactions of the CuC3H– and CuC3– cluster anions with CO have been studied by using mass spectrometry and theoretical calculations. The experimental results showed that the coupling of CO with the C3H– moiety of CuC3H– can generate the exclusive ion product COC3H–. The reactivity and selectivity of this reaction are greatly higher than that on the reaction of CuC3– with CO, and this H-assisted C?C coupling process was rationalized by theoretical calculations.

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Photo-induced proton coupled electron transfer (PCET) is essential in the biological, photosynthesis, catalysis and solar energy conversion processes. Recently, p-nitrophenylphenol (HO-Bp-NO<sub>2</sub>) has been used as a model compound to study the photo-induced PCET mechanism using ultrafast spectroscopy. In transient absorption spectra both singlet and triplet exhibited PCET behavior. When we focused on the PCET in the triplet state, a new sharp band attracted us. This band had not been observed for p-nitrobiphenyl which is without hydroxyl substitution. To assign the new band, acidic solutions were used as an additional proton donor. Based on results in strong (~10<sup>-1</sup> M) and weak (~10<sup>-4</sup> M) acidic solutions, the new band is identified as the open shell singlet O-Bp-NO<sub>2</sub>H, which is generated through protonation of nitro O in <sup>3</sup>HO-Bp-NO<sub>2</sub> followed by deprotonation of hydroxyl. Kinetics analysis indicates the formation of radical •O-Bp-NO<sub>2</sub> competes with O-Bp-NO<sub>2</sub>H in the way of concerted electron-proton transfer and/or proton followed electron transfers and is responsible for the low yield of O-Bp-NO<sub>2</sub>H. The results in the present work will make it clear that how the <sup>3</sup>HO-Bp-NO<sub>2</sub> deactivates in aprotic polar solvents and provide a solid benchmark for the deeply studying the PCET mechanism in triplets of analogous aromatic nitro compound.
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In recent decades, materials science has experienced rapid development and posed increasingly high requirements for the characterizations of structures, properties, and performances. Herein, we report on our recent establishment of a multi-domain (energy, space, time) high-resolution platform for integrated spectroscopy and microscopy characterizations, offering an unprecedented way to analyze materials in terms of spectral (energy) and spatial mapping as well as temporal evolution. We present several proof-of-principle results collected on this platform, including in-situ Raman imaging (high-resolution Raman, polarization Raman, low-wavenumber Raman), time-resolved photoluminescence imaging, and photoelectrical performance imaging. It can be envisioned that our newly established platform would be very powerful and effective in the multi-domain high-resolution characterizations of various materials of photoelectrochemical importance in the near future.
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Hydrogels show versatile properties and are of great interest in the fields of bioelectronics and tissue engineering. Understanding the dynamics of the water molecules trapped in the three-dimensional polymeric networks of the hydrogels is crucial for us to elucidate their mechanical and swelling properties at the molecular level. In this report, the poly(DMAEMA-co-AA) hydrogels were synthesized and characterized by the macroscopic swelling measurements under different pH conditions. Furthermore, the microscopic structural dynamics of pH stimulus responsive hydrogels were studied using FTIR and ultrafast IR spectroscopies from the viewpoint of the SCN-anionic solute as the local vibrational reporter. Ultrafast IR spectroscopic measurements showed the time constants of the vibrational population decay of SCN- were increased from 14±1 ps to 20±1 ps when the pH of the hydrogels is varied from 2.0 to 12.0. Rotational anisotropy measurements further revealed that the rotation of SCN- anionic probe was restricted by the three-dimensional network formed in the hydrogels and the rotation of SCN- anionic probe can’t decay to zero especially at the pH of 7.0. These results presented in this study are expected to provide molecular level understanding of the microscopic structure of the cross-linked polymeric network in the pH stimulus-responsive hydrogels.
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Among various photocatalytic materials, Z-scheme photocatalysts have drawn tremendous research interest due to the high photocatalytic performance in solar water splitting. Here, we perform extensive hybrid density functional theory calculations to explore electronic structures, interfacial charge transfer, electrostatic potential profile, optical absorption properties, and photocatalytic properties of a proposed two-dimensional small-lattice-mismatched GaTe/Bi2Se3 heterostructure. Theoretical results clearly reveal that the examined heterostructure with a small direct band gap can effectively harvest the broad spectrum of the incoming sunlight. Due to the relative strong interfacial built-in electric field in the heterostructure and the small band gap between the valence band maximum of GaTe monolayer and the conduction band minimum of Bi2Se3 nanosheet with slight band edge bending, the photogenerated carriers transfer via Z-scheme pathway, which results in the photogenerated electrons and holes effectively separating into the GaTe monolayer and the Bi2Se3 nanosheet for the hydrogen and oxygen evolution reactions, respectively. Our results imply that the artificial 2D GaTe/Bi2Se3 is a promising Z-scheme photocatalyst for overall solar water splitting.
The IRMPD spectrum of the protonated heterodimer of ProPheH+, in the range of 2700-3700 cm-1, has been obtained with a Fourier-transform ion cyclotron mass spectrometer combined with an IR OPO laser. The experimental spectrum shows one peak at 3560 cm?1 corresponding to the free carboxyl O-H stretching vibration, and two broad peaks centered at 2935 and 3195 cm?1. Theoretical calculations were performed on the level of M062X/6-311++G(d,p). Results show that the most stable isomer is characterized by a charge-solvated structure in which the proton is bound to the unit of Pro. Its predicted spectrum is in good agreement with the experimental one, although the coexistence of salt-bridged structures cannot be entirely excluded.
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A Mn3O4 coating is approved to modify the surface of LiNi0.5Mn1.5O4 particles by a simple wet grinding method for the first time, which realize an great improvement in electronic conductivity from 1.53?10-7 S cm-1 to 3.15?10-5 S cm-1 after 2.6% Mn3O4 coating. The electrochemical test resualts demonstrate that the Mn3O4 coating dramatically enhances both the rate performance and cycling capability (at 55 °C) of LiNi0.5Mn1.5O4. Among the samples, 2.6% Mn3O4-coated LiNi0.5Mn1.5O4 not only exhibits excellent rate capability (a large capacity of 108 mAh g-1 at 10 C rate) but also keep 78% capacity retention at 55 °C and 1 C rate after 100 cycles.
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Formaldehyde and hydrogen peroxide are two important realistic molecules in atmospheric chemistry. We implement path integral Liouville dynamics (PILD) to calculate the dipole-derivative autocorrelation function for obtaining the infrared (IR) spectrum. In comparison to exact vibrational frequencies, PILD faithfully capture most nuclear quantum effects in vibrational dynamics as temperature changes and as the isotopic substitution occurs.
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Two non-ionic hydro-fluorocarbon hybrid surfactants with and without hydroxyl groups were synthesized and compared. They exhibited good thermal stability and superior surface activity. It was observed that the hydroxyl group had a profound effect on modifying the surface tension of their solutions and the morphology of the formed micelles. This effect may be attributed to the rearranging of the alkane group from above the air/aqueous surface to below it and the disrupting of the interfacial water structure induced by the hydroxyl groups. This work provides a strategy to weaken the immiscibility between hydrocarbon and fluorocarbon chains by modifying their orientational structure at the interface, thus is helpful for the design of surfactants with varied interfacial properties.
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Empirical potential structure refinement (EPSR) is a neutron scattering data analysis algorithm and a software package. It was developed by the British spallation neutron source (ISIS) Disordered Materials Group in 1980s, and aims to construct the most-probable atomic structures of disordered materials in the field of chemical physics. It has been extensively used during the past decades, and has generated reliable results. However, it implements a shared-memory architecture with Open Multi-Processing (OpenMP). With the extensive construction of supercomputer clusters and the widespread use of graphics processing unit (GPU) acceleration technology, it is now possible to rebuild the EPSR with these techniques in the effort to improve its calculation speed. In this study, an open source framework NeuDATool is proposed. It is programmed in the object-oriented language C++, can be paralleled across nodes within a computer cluster, and supports GPU acceleration. The performance of NeuDATool has been tested with water and amorphous silica neutron scattering data. The test shows that the software can reconstruct the correct microstructure of the samples, and the calculation speed with GPU acceleration can increase by more than 400 times, compared with CPU serial algorithm at a simulation box that consists about 100 thousand atoms. NeuDATool provides another choice to implement simulation in the (neutron) diffraction community, especially for experts who are familiar with C++ programming and want to define specific algorithms for their analysis.
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In this paper, the effect of channel length and width on the large and small-signal parameters of the Graphene Field Effect Transistor (GFET) have been explored using an analytical approach. In the case of faster saturation as well as extremely high transit frequency GFET shows outstanding performance. From the transfer curve, it is observed that there is a positive shift of Dirac point from the voltage of 0.15 V to 0.35 V because of reducing channel length from 440 nm to 20 nm and this curve depicts that graphene shows ambipolar behavior. Besides, it is found that because of widening channel the drain current increases and the maximum current is found approximately 2.4 mA and 6 mA for channel width 2μm and 5μm respectively. Furthermore, an approximate symmetrical capacitance-voltage (C–V) characteristic of GFET is obtained and found that capacitance reduces when the channel length decreases but the capacitance can be increased by raising the channel width. In addition, a high transconductance of 6.4 mS at channel length 20 nm and 4.45 mS at channel width 5 μm along with a high transit frequency of 3.95 THz has been found that demands high-speed radio frequency (RF) applications.
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Two thin-film 2D organic–inorganic hybrid perovskites, i.e., 2-phenylethylammonium lead iodide (PEPI) and 4-phenyl-1-butylammonium lead iodide (PBPI) were synthesized and investigated by steady-state absorption, temperature-dependent photoluminescence, and temperature-dependent ultrafast transient absorption spectroscopy. PBPI has a longer organic chain (via introducing extra ethyl groups) than PEPI, thus its inorganic skeleton can be distorted bringing on structural disorder. The comparative analyses of spectral profiles and temporal dynamics revealed that the greater structural disorder in PBPI results in more defect states serving as trap states to promote exciton dynamics. In addition, the fine-structuring of excitonic resonances was unveiled by temperature-dependent ultrafast spectroscopy, suggesting its correlation with inorganic skeleton rather than organic chain. Moreover, the photoexcited coherent phonons were observed in both PEPI and PBPI, pointing to a subtle impact of structural disorder on the low-frequency Raman-active vibrations of inorganic skeleton. This work provides valuable insights into the optical properties, excitonic behaviors and dynamics, as well as coherent phonon effects in 2D hybrid perovskites.
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In this study, we have developed a high-sensitivity, near-infrared photodetector (NIRPD) based on PdSe2/GaAs heterojunction, which was made by transferring a multilayered PdSe2 film onto a planar GaAs. The as-fabricated PdSe2/GaAs heterojunction device exhibited obvious photovoltaic behavior to 808 nm illumination, indicating that the NIRPD can be used as a self-driven device without external power supply. Further device analysis showed that the hybrid heterojunction exhibited a high on/off ratio ratio of 1.16×105 measured at 808 nm under zero bias voltage. The responsivity and specific detectivity of photodetector were estimated to be 171.34 mA/W and 2.36×1011 Jones, respectively. Moreover, the device showed excellent stability and reliable repeatability. After 2 months, the photoelectric characteristics of the NIRPD hardly degrade in air, attributable to the good stability of the PdSe2. Finally, the PdSe2/GaAs-based heterojunction device can also function as a NIR light sensor.
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Over the last few years, machine learning is gradually becoming an essential approach for the investigation of heterogeneous catalysis. As one of the important catalysts, binary alloys have attracted extensive attention for the screening of bifunctional catalysts. Here we present a holistic framework for machine learning approach to rapidly predict adsorption energies on the surfaces of metals and binary alloys. We evaluate different machine-learning methods to understand their applicability to the problem and combine a tree-ensemble method with a compressed-sensing method to construct decision trees for about 60,000 adsorption data. Compared to linear scaling relations, our approach enables to make more accurate predictions lowering predictive root-mean-square error by a factor of two and more general to predict adsorption energies of various adsorbates on thousands of binary alloys surfaces, thus paving the way for the discovery of novel bimetallic catalysts.
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The simple homodinuclear M-M single bonds for Group II and XII elements are difficult to obtain as a result of the fulfilled s2 electronic configurations, consequently, a dicationic prototype is often utilized to design the M+-M+ single bond. Existing studies generally use sterically bulky organic ligands L- to synthesize the compounds in an L--M+-M+-L- manner. However, here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters, Mg2B7- and Zn2B7-, using density functional theory methods. The global minima of both of the clusters are in the form of M22+(B73-), where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety. Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters, which are driven by the unusually stable B73- moiety that is both σ and π aromatic. Vertical detachment energies of Mg2B7- and Zn2B7- are calculated to be 2.79 eV and 2.94 eV, respectively, for the future comparisons with experimental data.
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We carried out first-principles calculations to investigate the electronic properties of the monolayer blue phosphorene (BlueP) decorated by the group-IVB transition-metal adatoms (Cr, Mo and W), and found that the Cr-decorated BlueP is a magnetic half metal, while the Mo- andW-decorated BlueP are semiconductors with band gaps smaller than 0.2 eV. Compressive biaxial strains make the band gaps close and reopen and band inversions occur during this process, which induces topological transitions in the Mo-decorated BlueP (with strain of ??5:75%) and W-decorated BlueP (with strain of ??4:25%) from normal insulators to topological insulators (TIs). The TI gap is 94 meV for the Mo-decorated BlueP and 218 meV for the W-decorated BlueP. Such large TI gaps demonstrate the possibility to engineer topological phases in the monolayer BlueP with transition-metal adatoms at high temperature.
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We constructed two types of copper-doped metal–organic framework (MOF), i.e., Cu@UiO-66-NH2 and Cu-UiO-66-NH2. In the former, Cu2+ ions are impregnated in the pore space of the amine-functionalized, Zr-based UiO-66-NH2; while in the latter, Cu2+ ions are incorporated to form a bimetal-center MOF with Zr4+ being partially replaced by Cu2+ in the Zr–O oxo-clusters. Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state are promoted for both Cu-doped MOFs relative to undoped one, but in a sequence of Cu-UiO-66-NH2 > Cu@UiO-66-NH2 > UiO-66-NH2. Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs. These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system, further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.
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In this work, p-type Co3O4 decorated n-type ZnO (Co3O4/ZnO) nanocomposite was designed with the assistance of bacterial cellulose template. Phase composition, morphology and element distribution were investigated by XRD, SEM, HRTEM, EDS mapping and XPS. Volatile organic compounds (VOCs) sensing measurements indicated a noticeable improvement of response and decrease of working temperature for Co3O4/ZnO sensor, in comparison with pure ZnO, i.e., the response towards 100 ppm acetone was 63.7 (at a low working temperature of 180 °C), which was 26 times higher than pure ZnO (response of 2.3, at 240 °C). Excellent VOCs response characteristics could be ascribed to increased surface oxygen vacancy concentration (revealed by defect characterizations), catalytic activity of Co3O4 and the special p-n heterojunction structure, and bacterial cellulose provides a facile template for designing diverse functional heterojunctions for VOCs detection and other applications.
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The special mass shift coefficient, ΔKSMS, and field parameter factor, Ful of four multiples, 3〖s 〗^4 P→3〖p 〗^4 P^°, 3〖s 〗^4 P→3〖p 〗^4 D^°, 3〖s 〗^2 D→5〖p 〗^2 D^°, and 3〖s 〗^2 P→3〖p 〗^2 P^°, of 14N and 15N were studied using the multi-configuration Dirac–Hartree–Fock method and the relativistic configuration interaction approach. The normal mass shift, special mass shift, field shift, and isotope shift of N I were derived from the theoretical calculated ΔKSMS, ΔKSMS and Ful, and compared with the reported experimental measurements and theoretical results.
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The structures and electronic properties of the gaseous M2Pt20/? clusters (M represents the alkaline earth metal) are investigated using the density functional theory (B3LYP and PBE0) and wave function theory (SCS-MP2, CCSD and CCSD (T)). The results show that the D2h isomers with the planar structures are more stable than the C2V isomers with smaller dihedral angles and shorter Pt-Pt bond lengths. In this work we show that the mutual competition of M(s, p)-Pt(5d) interaction and Pt-Pt covalent bonding contributes to the different stabilizations of the two kinds of isomers. The M(s, p)-Pt(5d) interaction favors the planar isomers with D2h symmetry, while the Pt-Pt covalent bonding leads to the C2V isomers with bending structures. Two different crossing points are determined in the potential energy curves of Be2Pt2 with the singlet and triplet states. But there is just one crossing point in potential energy curves of Ra2Pt2 and Ca2Pt2? because of flatter potential energy curves of Ra2Pt2 with the triplet state or Ca2Pt2? with quartet state. The results reveal a unique example of dihedral angle-bending isomers with the smallest number of atoms and may help the understanding of the bonding properties of other potential angle-bending isomers.
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From the organization of animal ocks to the emergence of swarming behav- iors in bacterial suspension, populations of motile organisms at all scales display coherent collective motion. Recent studies showed the anisotropic interaction between the active particles plays a key role on the phase behaviors. Here we investigate the collective behaviors of active Janus particles that experience an anisotropic interaction that is opposite to the active force by using Langevin dynamics simulations in two dimensional space. Interestingly, the system shows emergence of collective swarming states upon increasing the total area fraction of particles, which is not observed for systems without anisotropic interaction or activity. The threshold value of area fraction c decreases with particle ac- tivity or interaction strength. We have also performed basic kinetic analysis to reproduce the essential features of the simulation results. Our results demon- strate that anisotropic interactions at the individual level are sucient to set homogeneous active populations into stable directed motion.
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Photocatalytic degradation of organic pollutants has become a hot research topic because of its low energy consumption and environmental-friendly characteristics. Bismuth oxide (Bi2O3) nanocrystals with a bandgap ranging between 2.0-2.8 eV has attracted increasing attention due to high activity of photodegradation of organic pollutants by utilizing visible light. Though several methods have been developed to prepare Bi2O3-based semiconductor materials over recent years, it is still difficult to prepare highly active Bi2O3 catalysts in large-scale with a simple method. Therefore, developing simple and feasible methods for the preparation of Bi2O3 nanocrystals in large-scale is important for the potential applications in industrial wastewater treatment. In this work, we successfully prepared porous Bi2O3 in large scale via etching commercial BiSn powders, followed by thermal treatment with air. The acquired porous Bi2O3 exhibited excellent activity and stability in photocatalytic degradation of methylene blue (MB). Further investigation of the mechanism witnessed that the suitable band structure of porous Bi2O3 allowed the generation of reactive oxygen species, such as O2-? and ?OH, which effectively degraded MB.
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The structure-property relationship of DAE-derivative (C5F-4Py) molecular isomers which involve ring-closed status and ring-open status is investigated by employing non-equilibrium Green’s function formalism combined with density functional theory. Molecular junctions are formed by the isomers connecting to Au (111) electrodes through the flanked pyridine groups. The difference of electronic structures caused by different geometry structures for the two isomers, especially the alternative single bond and double bond in ring-closed molecule, contributes the remarkable different low-bias conductance values. The LUMO orbitals of isomers are mainly channels to transport electron. In addition, the more electrons transferred to ring-closed molecular junction in equilibrium condition drop down the LUMO orbitals closer to the Fermi energy which may be to contribute larger conductance value at Fermi level. Our findings are help to understand the mechanism of the low-bias conducting mechanism of and are conductive to design of high performance molecular switching based on DAE or DAE-derivatives molecules.
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Multinanoparticles interacting with the phospholipid membranes in solution were studied by dissipative particle dynamics simulation. The nanoparticles selected have spherical or cylindrical shapes, and they have various initial velocities in the dynamical processes. Several translocation modes are defined according to their characteristics in the dynamical processes, in which the phase diagrams are constructed based on the interaction strengths between the particles and membranes and the initial velocities of particles. Furthermore, several parameters, such as the system energy and radius of gyration, are investigated in the dynamical processes for the various translocation modes. Results elucidate the effects of multiparticles interacting with the membranes in the biological processes.
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Surface passivation is one valuable approach to tune the properties of nanomaterials. The piezo- electric properties of hexagonal [001] ZnO nanowires with four kinds of surface passivations were investigated using the rst-principles calculations. It is found that in the 50% H(O), 50% Cl(Zn); 50% H(O), 50% F(Zn) passivations, the volume and surface e ects both enhance the piezoelectric coecient. This di ers from the unpassivated cases where the surface e ect was the sole source of piezoelectric enhancement. In the 100% H; 100% Cl passivations, the piezoelectric enhancement is not possible since the surface e ect is screened by surface charge with weak polarization. The study reveals that the competition between the volume e ect and surface e ect in uences the iden- ti cation of the diameter-dependence phenomenon of piezoelectric coecients for ZnO nanowires in experiments. Moreover, the results suggest that one e ective means of improving piezoelectricity of ZnO nanowires is shrinking axial lattice or increasing surface polarization through passivation.
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A distributed feedback (DFB) laser with a wavelength of 2.8 m was used to measure the species produced by water vapor glow discharge. Only the absorption spectra of OH radicals and transient H2O molecules were observed using concentration modulation (CM) spectroscopy. The intensities and orientations of the absorption peaks change with the demodulation phase, but the direction of one absorption peak of H2O is always opposite to the other peaks. The different spectral orientations of OH and H2O reflect the increase or decrease of the number of particles in the energy levels. If more transient species can be detected in the discharge process, the dynamics of excitation, ionization and decomposition of H2O can be better studied. This study shows that the demodulation phase relationship of CM spectrum can be used to study the population change of molecular energy levels.
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A new kind of phenyl-functionalized magnetic fibrous mesoporous silica (Fe3O4@SiO2@KCC-1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe3O4@SiO2@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response (29 emu g–1), and an abundant π-electron system, which allowed rapid isolation of the Fe3O4@SiO2@KCC-1-phenyl from solutions upon applying an appropriate magnetic field. Several variables that affect the extraction efficiency of the analytes, including the type of the elution solvent, amount of adsorbent, extraction time and reusability, were investigated and optimized. Under optimum conditions, the Fe3O4@SiO2@KCC-1-phenyl was used for the extraction of four phthalate esters from environmental water samples followed by high-performance liquid chromatographic analysis. Validation experiments indicated that the developed method presented good linearity (0.1–20 ng mL-1), low limit of detection (7.5-29 μg L–1, S/N=3). The proposed method was applied to the determination of phthalate esters in different real water samples, with relative recoveries of 93-103.4% and RSDs of 0.8–8.3 %.
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Developing low-cost and high-efficient noble-metal-free cocatalysts has been a challenge to achieve economic hydrogen production. In this work, molybdenum oxides (MoO3-x) were in-situ loaded on polymer carbon nitride (PCN) via a simple one-pot impregnation-calcination approach. Different from post-impregnation method, intimate coupling interface between high-dispersed ultra-small MoO3-x nanocrystal and PCN was successfully formed during the in-situ growth process. The MoO3-x-PCN-x photocatalyst without noble platinum (Pt) finally exhibited enhanced photocatalytic hydrogen performance under visible light irradiation (λ>420 nm), with the highest hydrogen evolution rate of 15.6 μmol/h, which was more than 3 times that of bulk PCN. Detailed structure-performance revealed that such improvement in visible-light hydrogen production activity originated from the intimate interfacial interaction between high-dispersed ultra-small MoO3-x nanocrystal and polymer carbon nitride as well as efficient charge carriers transfer brought by Schottky junction formed.
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[Abstract](330)
Highly luminescent bulk two-dimensional covalent organic frameworks (COFs) attract much attention recently. Origin of their luminescence and their large Stokes shift is an open question. After first-principles calculations on two kinds of COFs using the GW method and Bethe-Salpeter equation, we find that monolayer COF has a direct band gap, while bulk COF is an indirect band-gap material. The calculated optical gap and optical absorption spectrum for the direct excitons of bulk COF agree with the experiment. However, calculated energy of the indirect exciton, in which the photoelectron and the hole locate at the conduction band minimum and the valence band maximum of bulk COF respectively, is too low compared to the fluorescence spectrum in experiment. This may exclude the possible assistance of phonons in the luminescence of bulk COF. Luminescence of bulk COF might result from exciton recombination at the defects sites. The indirect band-gap character of bulk COF originates from its AA-stacked conformation. If the conformation is changed to the AB-stacked one, the band gap of COF becomes direct which may enhance the luminescence.
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The geometric structures and vibration frequencies of para-chlorofluorobenzene (p-ClFPh) in the first excited state of neutral and ground state of cationic were investigated by resonance-enhanced multiphoton ionization (REMPI) and slow electron velocity-map imaging (SEVI). The infrared spectrum of S0 state and absorption spectrum for S1 ← S0 transition in p-ClFPh were also recorded. Based on the one-color resonant two-photon ionization (1C-R2PI) spectrum and two-color resonant two-photon ionization (2C-R2PI) spectrum, we measured the adiabatic excitation energy of p-ClFPh as 36302 ± 4 cm-1. In the 2C-R2PI SEVI spectra, the accurate adiabatic ionization potential (AIP) of p-ClFPh was extrapolated to be 72937 ± 8 cm?1 via a series of progressive measurements near threshold ionization region. In addition, Franck-Condon simulations were performed to help us confidently ascertain the main vibration modes in the S1 and D0 states. The wavenumber changes of vibration modes during the transition of S1 ← S0 and D0 ← S1 were discussed. Furthermore, the mixing of vibration modes both between S0 & S1 and S1 & D0 has been analyzed.
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The geometric and electronic structures of several possible adsorption configurations of the pyrazine (C4H4N2) molecule covalently attached to Si(100) surface, which is of vital importance in fabricating functional nanodevices, have been investigated using X-ray spectroscopies. The Carbon K-shell (1s) X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of predicted adsorbed structures have been simulated by density functional theory (DFT) with cluster model calculations. Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations. In contrast to the XPS spectra, it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100) systems can be well utilized for structural identification, which has been discussed in detail in this article. In addition, according to the classification of carbon atoms, the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.
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Cancer is one of the most serious issues in human life. Blocking Programmed cell death protein 1 (PD-1) and programmed death ligand-1 (PD-L1) pathway is one of the great innovation on last few years, but a few numbers of inhibitors can be able to block it. (2-methyl-3-biphenylyl) methanol (MBPM) derivative is one of them. Here, the quantitative structure-activity relationship (QSAR) established twenty (2-methyl-3-biphenylyl) methanol (MBPM) derivatives as the programmed death ligand-1 (PD-L1) inhibitors. Density functional theory (DFT) at the B3LPY/6-31+G (d, p) level was employed to study the chemical structure and properties of the chosen compounds. Highest occupied molecular orbital energy EHOMO, lowest unoccupied molecular orbital energy ELUMO, total energy ET, dipole moment DM, absolute hardness η, absolute electronegativity χ, softness S, electrophilicity ω, energy gap ΔE, etc, properties were observed and determine. Principal component analysis (PCA), multiple linear regression (MLR) and multiple non-linear regression (MNLR) analysis were carried out to establish the QSAR. The proposed quantitative models and interpreted outcomes of the compounds were based on statistical analysis. Statistical results of MLR and MNLR exhibited the coefficient was 0.661 and 0.758, respectively. Leave-one-out cross-validation (LOO-CV), r2m metric, r2m test and “Golbraikh & Tropsha’s criteria” analyses were applied for the validation of MLR and MNLR, which indicate two models are statistically significant and well stable with data variation in the external validation towards PD-L1. The obtained values specified that the two different modelings can predict the bioactivity and may be helpful and supporting for evaluation of the biological activity of PD-L1 inhibitor.
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Zinc oxide is recently being used as magnetic semiconductor with introduction of magnetic elements in it. In this work, we report phase pure synthesis of Mg and Ni co-substituted ZnO to explore its structure, optical, magnetic and photo-catalytic properties. X-ray diffraction analysis reveal the formation of hexagonal wurtzite type structure having P63mc space group without any impurity phase. UV-Vis spectrophotometry demonstrate the variation in band gap with addition of Mg and Ni content in ZnO matrix. Magnetic measurements exhibit a clear boosted magnetization in Ni and Mg co-doped compositions with its stable value of band gap corroborating the structural stability and magnetic tuning for its advanced applications in modern day spintronic devices. Photo-catalytic measurements were performed using methyl green degradation demonstrate an enhanced trend of activity in Mg and Ni co-doped compositions.
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ATP-binding cassette (ABC) exporters transport many substrates out of cellular membranes via alternating between inward-facing (IF) and outward-facing (OF) conformations. Despite extensive research efforts over the past decades, understanding of the molecular mechanism remains elusive. As these large-scale conformational movements are global and collective, we have previously performed extensive coarse-grained molecular dynamics (CG-MD) simulations of the potential of mean force (PMF) along the conformational transition pathway [Z. Wang et. al JPCB, 119, 1295?1301 (2015)]. However, the occluded (OC) conformational state, in which both the internal and external gate are closed, was not determined in the calculated free energy profile. In this paper, we extend the above methods to the calculation of the free energy profile along the reaction coordinate, d1- d2, which are the COM distances between the two sides of the internal (d1) and the external gate (d2). The PMF is thus obtained to identify the transition pathway, along which several OF-, IF- and OC- state structures are predicted in good agreement with structural experiments. Our CG-MD free-energy simulations demonstrate that the internal gate is closed before the external gate is open during the IF to OF transition and vice versa during the IF to OF transition. Our results capture the unidirectional feature of substrate translocation via the exporter, which is functionally important in biology. This finding is different from the results, in which both the internal and external gates are open reported in an X-ray experiment [Ward A. et al, PNAS, 104, 19005?19010 (2007)]. Our study sheds light on the molecular mechanism of the state transitions in the ABC exporter.