2008 Vol. 21, No. 3

We show that by scanning the frequency of a single mode infrared (IR) optical parametric oscillator (IR-OPO) laser to excite the molecular species of interest and fixing the frequency of a vacuum ultraviolet (VUV) laser to photoionize the IR excited species, high-resolution IR spectra of polyatomic neutrals can be obtained with high sensitivity. The fact that this IR-VUV-photoion (IR-VUV-PI) method is based on VUV photoionization probe, and thus, allows the identification of the neutral IR absorber, makes it applicable for IR spectroscopy measurements of isotopemers, radicals, and clusters, which usually exist as impure samples. The highly resolved IR-VUV-PI measurements achieved using the single mode IR-OPO laser have made possible the selection of single rovibrational states of CH3X (X=Br and I), C2H4, and C3H4 for VUV-pulsed field ionization-photoelectron (VUV-PFI-PE) measurements, resulting in rovibrationally resolved photoelectron spectra for these polyatomic molecules. These experiments show that the signal-to-noise ratios of the IR-VUV-PI and IR-VUV-PFI-PE spectra obtained by employing the high-resolution IR-OPO laser are significantly higher than those observed in previous IR-VUV-PI and IR-VUV-PFI-PE studies using a low-resolution IR-OPO laser. Further improvement in sensitivity of IR-VUV-PI and IR-VUV-PFI-PE measurements by using the collinear arrangement of IR-VUV lasers and molecular beam is discussed.
It was reported on the elimination of interfering absorption of BTX. the absorption of O2 includes different absorption bands, which change differently when the partial pressure of oxygen is varied. These cause the nonlinear absorption of O2 and the observed band shape to vary with the column density of O2. The absorption ratios of molecular absorption in each of the Herzberg bands and dimer absorptions, as well as the contribution to the correction error of molecular absorption, are studied based on the characteristic of these absorption bands. The optimized way to eliminate the interfering absorption is obtained in the end and the effectiveness of using interpolation proposed by Volkamer et al. to remove O2 absorption is proved again. As to O3 and SO2, the effect of the thermal effect of characteristic spectra on the elimination error of their absorption is studied. Solutions to these problems are discussed and demonstrated together with methods to optimize the interpolation of spectra. As a sample application, differential optical absorption spectroscopy (DOAS) measurements of BTX are carried out. Results show a low detection limit and the good correlation with point instruments are achieved. All these prove the feasibility of using spectral interpolation to improve the accuracy of DOAS measurements of aromatic hydrocarbons for practical purposes.
The internal conversion (IC) processes of chlorophyll a (chl-a) in solvents are studied based on the reduced density matrix theory. The IC times can be obtained by simulating the experimental fluorescence depletion spectra (FDS). The calculated IC times of chl-a in ethyl acetate, tetrahydrofuran and dimethyl formamide are 141, 147, and 241 fs, respectively. The oscillation feature of the FDS results from the forward and backward transfer of the population between coupled electronic states. The effects of diabatic coupling between two electronic states on the IC time and the FDS are described. The influence of molecule-reservoir coupling on the IC time is also investigated.
Allergic contact dermatitis is a delayed hypersensitivity reaction, which results from skin exposure to low molecular weight chemicals such as haptens. To clarify the pathogenic mechanism, electrospray ionization mass spectrometry (ESI-MS) and hydrogen/deuterium (H/D) exchange, as well as UV spectroscopy, were applied to determine the interaction between the model protein cytochrome c (cyt c) and the hapten 2,4-dinitro-fluorobenzene (DNFB). The ESI-MS results demonstrate that the conformation of cyt c can change from native folded state into partially unfolded state with the increase of DNFB. The equilibrium state H/D exchange followed by ESI-MS further confirms the above results. UV spectroscopy indicates that the strongfield coordination between iron of heme (prosthetic group) and His18 or Met80 of cyt c is not obviously affected by the hapten.
N,N-dimethylacetamide (DMA) has been investigated extensively in studying models of peptide bonds. An all-atom MD simulation and the NMR spectra were performed to investigate the interactions in the DMA-water system. The radial distribution functions (RDFs) and the hydrogen-bonding network were used in MD simulations. There are strong hydrogen bonds and weak C-H¢ ¢ ¢O contacts in the mixtures, as shown by the analysis of the RDFs. The insight structures in the DMA-water mixtures can be classified into different regions by the analysis of the hydrogen-bonding network. Chemical shifts of the hydrogen atom of water molecule with concentration and temperatures are adopted to study the interactions in the mixtures. The results of NMR spectra show good agreement with the statistical results of hydrogen bonds in MD simulations.
Three novel nonlinear chromophores with symmetric D-π-D molecular structure and extended conjugated length were synthesized. Solvatochromism analysis shows great symmetric intramolecular charge transfer occurring in chromophores by the enhancement in the dipole moment between the ground and excited states. The properties of optical power limiting induced by three-photon absorption (3PA) are demonstrated. Large 3PA coefficients and the corresponding molecular cross sections as high as 10-74 cm6s2 were obtained for nanosecond laser pulses at 1.06 μm from nonlinear transmission measurements.
Er3+ doped SrTiO3 ultrafine powders were prepared by solid state reaction in a molten NaCl flux. The structural properties were characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared spectroscopy. The Stokes emission spectra of Er3+ in SrTiO3:Er3+ ranging from green to near infrared region were investigated under 514.5 nm laser excitation. The green and redupconverted luminescence spectra of Er3+ were measured under excitation into the 4I9=2 level by 785 nm laser. The upconversion mechanisms were studied in detail through laser power dependence and Er3+ ion concentration dependence of upconverted emissions, and results show that excited state absorption and energy transfer process are the possible mechanisms for the upconversion. The upconversion properties indicate that SrTiO3:Er3+ may be used in upconversion phosphors.
The reaction system of 1-propenyl radical with NO is an ideal model for studying the intermolecular and intramolecular reactions of complex organic free radicals containing C=C double bonds. On the basis of the full optimization of all species with the Gaussian 98 package at the B3LYP/6-311++G** level, the reaction mechanism was elucidated extensively using the vibrational mode analysis. There are seven reaction pathways and five sets of small molecule end products: CH2O+CH3CN, CH2CHCN+H2O, CH3CHO+HCN, CH3CHO+HNC, and CH3CCH+HNO. The channel of C3H5¢+NO→ IM1→TS1→IM2→TS2→IM3→TS3→CH3CHO+HCN is thermodynamically most favorable.
A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD(T) methods with the 6-311+G(d,p) and the 6-311++G(d,p) basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between Al and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.
An assumptive theoretical relationship is suggested to describe the property of molecular atomization energy and energy transfer rate in the initiation of explosions. To investigate the relationship between atomization energy and energy transfer rate, the number of doorway modes of explosives is estimated by the theory of Dlott and Fayer in which the rate is proportional to the number of normal mode vibrations. It was evaluated frequencies of normal mode vibrations of eight molecules by means of density functional theory (DFT) at the b3p86/6-31G(d,p) level. It is found that the number of doorway modes shows a linear correlation to the atomization energies of the molecules, which were also calculated by means of the same method. A mechanism of this correlation is discussed. It is also noted that in those explosives with similar molecular structure and molecular weight, the correlation between the atomization energy and the number of doorway modes is higher.
Haloacetonitrile anions CH2XCN- (X=F, Cl) were studied by HF-SCF, Becke3-LYP, and MP2 methods together with the Dunning's basis set aug-cc-PVTZ. The vertical electron attachments to the neutral are endothermic. The geometrically optimized CH2FCN- is mainly a valence-bounded anion and CH2FCN-→CH2CN+F- is a nonadiabatic dissociation. This theoretical study in good agreement with the experimental results shows that the Becke3-LYP method is reasonable in describing the electronic structures of anions and dissociative attachment dynamics, while significant differences between MP2 and Becke3-LYP results are shown for the dissociation potential curves of CH2ClCN-→CH2CN+Cl-.2,70-(Ethylene)-bis-8-hydroxyquinoline was optimized with DFT/B3LYP and ab initio HF methods, so ionization potential and electron affinity could be determined. Absorption spectrum was calculated by ZINDO and TD-DFT. CIS method was used to calculate the S1 excited states of the compound and afterwards the emission spectrum was computed. When the solvent effect was taken into account, the computed results show encouraging agreement with known experimental data. The results of analyzing the relationship between the energies and absorption spectra indicate that the ability to transporting electrons is strengthened compared with 8-hydroxyquinoline and that absorption and emission spectra are red-shifted. The intramolecular reorganization energy of tris(2,70-(ethylene)-bis-8-hydroxyquinoline)-aluminum implies its electron transporting property is worse than tris(8-hydroxyquinoline)-aluminum. The predicted maximum emission wavelength is red-shifted compared with tris(8-hydroxyquinoline)-aluminum.
Dielectric relaxation method was employed to study the properties of oxygen ion diffusion and phase transition in the oxide-ion conductors (La1-xLnx)2Mo2O9 (Ln=Nd, Gd, x=0.05-0.25). Two dielectric loss peaks were observed: peak Pd at about 600 K and peak Ph around 720 K. Peak Pd is a relaxational peak and associated with the short-range diffusion of oxygen ions, while peak Ph hardly changes its position and dramatically decreases in height with increasing frequency, exhibiting non-relaxational nature. With increasing Ln3+ concentration, the heights of peak Ph and Pd increase at first and then decrease after passing a maximum at 15% doping. It is suggested that peak Ph is related to the phase transition of a static disordered state to a dynamic disordered state in oxygen ions/vacancies distribution. It is found that the 15%Gd or 15%Nd doped La2Mo2O9 samples exhibit the highest conductivity in accordance with the highest height of peak Pd at this doping content.
Monte Carlo simulations were used to study the translocation of a flexible polymer through a pore in a membrane, assuming an attractive interaction between the monomers and the membrane on the trans side of the membrane and no interaction on the cis side. For the case TTc, τ increases with increasing temperature. The translocation time depends on the absorbed energy u0 in a nontrivial way. The value of τ increases initially upon increasing u0 before it begins to decrease.
The variation of the translocation time with respect to the solvent quality was also studied. It showed that there is a transition, as the solvent quality improves from \poor to \good: when ABc, τ increases with increasing AB. When the chain length was changed, it was found that when the absorbed energy u0 was greater than uc, τ was proportional to N1:602; for u0
A part of a long DNA chain was driven into a confined environment by an electric field, while the rest remains in the higher-entropy region. Upon removal of the field, the chain recoils to the higher-entropy region spontaneously. This dynamical process was investigated by Monte Carlo simulations. The simulation reproduces the experimentally-observed phenomenon that the recoil of the DNA chain is initially slow and gradually increases in speed due to the presence of the confinement-entropic force. The results show that with increasing the dimension or decreasing the spacing of the nanopillars the recoil velocity of the DNA chain will increase. Further analysis suggests that the characteristic entropy per monomer in the confinement is proportional to the area fraction of the free part in the confinement.
BaCe0.8Pr0.2O3-α ceramic was synthesized by high temperature solid-state reaction. The structural characteristics and the phase purity of the crystal were determined using powder X-ray diffraction analysis. By using the methods of AC impedance spectroscopy, gas concentration cell and electrochemical pumping of hydrogen, the conductivity and ionic transport number of BaCe0.8Pr0.2O3-α were measured, and the electrical conduction behavior of the material was investigated in different gases in the temperature range of 500-900 ffiC. The results indicate that the material was of a single perovskite-type orthorhombic phase. From 500 ffiC to 900 ffiC, electronic-hole conduction was dominant in dry and wet oxygen, air or nitrogen, and the total conductivity of the material increased slightly with increasing oxygen partial pressure in the oxygen partial pressure range studied. Ionic conduction was dominant in wet hydrogen, and the total conductivity was about one or two orders of magnitude higher than that in hydrogen-free atmosphere (oxygen, air or nitrogen).
The effect of salt concentration on layer-by-layer deposition of poly(sodium 4-styrene sulfonate) (PSSS)/poly(vinylbenzyl trimethylammonium chloride) (PVTC) was investigated by use of quartz crystal microbalance with dissipation (QCM-D). The changes in frequency and dissipation demonstrate that the addition of NaCl leads the thickness of PSSS/PVTC multilayer to increase. The deposition of PSSS/PVTC is dominated by surface charge overcompensation level at lower salt concentrations. However, it is mainly determined by the interpenetration of polyelectrolytes at a higher salt concentration, as reflected in the oscillation of dissipation change.
BaTiO3 nanocrystals were synthesized by sol-gel method using barium acetate (Ba(CH3COO)2) and tetrabutyl titanate (Ti(OC4H9)4) as raw materials. Xerogel precursors and products were characterized by means of thermogravimetric/differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD) and transmission electron microscope (TEM). The influence of the calcination temperature and duration on the lattice constant, the lattice distortion, and the grain size of BaTiO3 nanocrystals was discussed based on the XRD results. The grain growth kinetics of BaTiO3 nanocrystals during the calcination process were simulated with a conventional grain growth model which only takes into account diffusion, and an isothermal model proposed by Qu and Song, which takes into account both diffusion and surface reactions. Using these models, the pre-exponential factor and the activation energy of the rate constant were estimated. The simulation results indicate that the isothermal model is superior to the conventional one in describing the grain growth process, implying that both diffusion and surface reactions play important roles in the grain growth process.