2020 Vol. 33, No. 6

2020, 33(6): i-iv.
2020, 33(6): v-vi.
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.
Stars with masses between 1 and 8 solar masses (M$_\odot$) lose large amounts of material in the form of gas and dust in the late stages of stellar evolution, during their Asymptotic Giant Branch (AGB) 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 in the presence of a stellar companion, such as a white dwarf star, the high flux of UV photons destroys H$_2$O 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.
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.
The special mass shift coefficient and field parameter factor of four multiples, 3s$^4$P$\rightarrow$3p$^4$P$^\circ$, 3s$^4$P$\rightarrow$3p$^4$D$^\circ$, 3s $^2$D$\rightarrow$5p $^2$D$^\circ$, and 3s $^2$P$\rightarrow$3p $^2$P$^\circ$, of $^{14}$N and $^{15}$N were studied using the multi-configuration Dirac-Hartree-Fock method and the relativistic configuration interaction approach. The normal mass shifts, special mass shifts, field shifts, and isotope shifts of N(Ⅰ) were derived from the theoretical calculated normal mass shift parameter, special mass shift parameter and field parameter factor, and compared with the reported experimental measurements and theoretical results.
The vacuum ultraviolet photodissociation of OCS via the $F$ $3^1\Pi$ Rydberg states was investigated in the range of 134$-$140 nm by means of the time-sliced velocity map ion imaging technique. The images of S($^1$D$_2$) products from the CO($X^1\Sigma^+$)+S($^1$D$_2$) dissociation channel were acquired at five photolysis wavelengths, corresponding to a series of symmetric stretching vibrational excitations in OCS($F$ $3^1\Pi$, $v_1$=0$-$4). The total translational energy distributions, vibrational populations and angular distributions of CO($X^1\Sigma^+$, $v$) coproducts were derived. The analysis of experimental results suggests that the excited OCS molecules dissociate to CO($X^1\Sigma^+$) and S($^1$D$_2$) products via non-adiabatic couplings between the upper $F$ $3^1\Pi$ states and the lower-lying states both in the C$_{\infty \textrm{v}}$ and C$_{\rm{s}}$ symmetry. Furthermore, strong wavelength dependent behavior has been observed: the greatly distinct vibrational populations and angular distributions of CO($X^1\Sigma^+$, $v$) products from the lower ($v_1$=0$-$2) and higher ($v_1$=3, 4) vibrational states of the excited OCS($F$ $3^1\Pi$, $v_1$) 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 vacuum ultraviolet photodissociation dynamics.
The structure-property relationship of diarylethene (DAE)-derivative molecular isomers, which involve ring-closed and ring-open forms, is investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Molecular junctions are formed by the isomers connecting to Au(111) electrodes through flanked pyridine groups. The difference in electronic structures caused by different geometry structures for the two isomers, particularly the interatomic alternative single bond and double bond of the ring-closed molecule, contributes to the vastly different low-bias conductance values. The lowest unoccupied molecular orbital (LUMO) of the isomers is the main channel for electron transport. In addition, more electrons transferred to the ring-closed molecular junction in the equilibrium condition, thereby decreasing the LUMO energy to near the Fermi energy, which may contribute to a larger conductance value at the Fermi level. Our findings are helpful for understanding the mechanism of low-bias conductance and are conducive to the design of high-performance molecular switching based on diarylethene or diarylethene-derivative molecules.
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 60000 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.
ATP-binding cassette exporters transport many substrates out of cellular membranes via alternating between inward-facing and outward-facing 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 simulations of the potential of mean force along the conformational transition pathway [J. Phys. Chem. B 119 , 1295 (2015)]. However, the occluded conformational state, in which both the internal and external gate are closed, was not determined in the calculated free energy profile. In this work, we extend the above methods to the calculation of the free energy profile along the reaction coordinate, $d_1$$-$$d_2$, which are the COM distances between the two sides of the internal ($d_1$) and the external gate ($d_2$). The potential of mean force is thus obtained to identify the transition pathway, along which several outward-facing, inward-facing, and occluded state structures are predicted in good agreement with structural experiments. Our coarse-grained molecular dynamics free-energy simulations demonstrate that the internal gate is closed before the external gate is open during the inward-facing to outward-facing transition and vice versa during the inward-facing to outward-facing 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 previous result, in which both the internal and external gates are open reported in an X-ray experiment [Proc. Natl. Acad. Sci. USA 104 , 19005 (2007)]. Our study sheds light on the molecular mechanism of the state transitions in an ATP-binding cassette exporter.
From the organization of animal flocks to the emergence of swarming behaviors in bacterial suspension, populations of motile organisms at all scales display coherent collective motion. Recent studies showed that the anisotropic interaction between active particles plays a key role in the phase behaviors. Here we investigate the collective behaviors of based-active Janus particles that experience an anisotropic interaction of which the orientation is opposite to the direction of 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 in systems without anisotropic interaction or activity. The threshold for emergence of swarming states decreases as particle activity or interaction strength increases. We have also performed basic kinetic analysis to reproduce the essential features of the simulation results. Our results demonstrate that anisotropic interactions at the individual level are sufficient to set homogeneous active particles into stable directed motion.
Empirical potential structure refinement is a neutron scattering data analysis algorithm and a software package. It was developed by the disordered materials group in the British spallation neutron source (ISIS) 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 has 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.
In this study, we have developed a high-sensitivity, near-infrared photodetector based on PdSe$_2$/GaAs heterojunction, which was made by transferring a multilayered PdSe$_2$ film onto a planar GaAs. The as-fabricated PdSe$_2$/GaAs heterojunction device exhibited obvious photovoltaic behavior to 808 nm illumination, indicating that the near-infrared photodetector 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 of 1.16$\times$10$^5$ 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$\times$10$^{11}$ Jones, respectively. Moreover, the device showed excellent stability and reliable repeatability. After 2 months, the photoelectric characteristics of the near-infrared photodetector hardly degrade in air, attributable to the good stability of the PdSe$_2$. Finally, the PdSe$_2$/GaAs-based heterojunction device can also function as a near-infrared light sensor.
Zinc oxide is recently being used as a magnetic semiconductor with the introduction of magnetic elements. 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 reveals the hexagonal wurtzite type structure having P63mc space group without any impurity phase. UV-Vis spectrophotometry demonstrates the variation in bandgap with the 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 bandgap corroborating the structural stability and magnetic tuning for its advanced applications in modern-day spintronic devices. Photo-catalytic measurements performed using methyl green degradation demonstrate an enhanced trend of activity in Mg and Ni co-doped compositions.
A new kind of phenyl-functionalized magnetic fibrous mesoporous silica (Fe$_3$O$_4$@SiO$_2$@KCC- 1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe$_3$O$_4$@SiO$_2$@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response (29 emu/g), and an abundant $\pi$-electron system, which allowed rapid isolation of the Fe$_3$O$_4$@SiO$_2$@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 Fe$_3$O$_4$@SiO$_2$@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), low limit of detection (7.5-29 µg/L, $S/N$=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 relative standard deviation of 0.8%-8.3%.
The effect of channel length and width on the large and small-signal parameters of the graphene field effect transistor have been explored using an analytical approach. In the case of faster saturation as well as extremely high transit frequency, the graphene field effect transistor 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 2 μm and 5 μm respectively. Furthermore, an approximate symmetrical capacitance-voltage ($C-V$) characteristic of the graphene field effect transistor is obtained and the capacitance reduces when the channel length decreases but the capacitance can be increased by raising the channel width. In addition, a high transconductance, that demands high-speed radio frequency (RF) applications, 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 have been found that demands high-speed radio frequency applications.
The influence of various water soluble cations (K$^+$, Na$^+$, Ca$^{2+}$, Mg$^{2+}$) on the hydration of calcined flue gas desulphurization gypsum was investigated. The results show that all cations but Ca$^{2+}$ can accelerate the hydration of bassanite. The final crystal size is not largely influenced by different salts, except for Na$^+$, where the giant crystal with length of $>$130 μm is observed. Current study clarifies the influence of different ions on the hydration of bassanite, which could provide sufficient guide for the pre-treatment of original flue gas desulphurization gypsum before actual application.
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 tetramethylammonium hydroxide (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. 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. This new etching method is of great significance in the low-cost and high-quality micro-electro-mechanical system industrial fabrication.