Theoretical study of LiCl− and LiBr− molecular ions

The molecular structures and spectroscopic constants of the ground electronic states of LiCl^? and LiBr^? are investigated with the coupled-cluster method. To improve the accuracy of our calculations, we have employed the extrapolation schemes as well as corrections of the core–valence correlation and scalar relativistic effect. The equilibrium parameters, potential energy curves, force constants, vibrational energy levels and spectroscopic parameters of both molecular ions are derived, in which those of LiBr^? are reported for the first time. The electron affinities and vertical detachment energies of neutral and anionic LiCl and LiBr are also evaluated.     

Mechanistic study of the reaction of methyl peroxy radical (CH3O2) with formaldehyde (CH2O)

ABSTRACT

A direct dynamic study on the reactions of CH₃O₂?+?CH₂O was carried out over the temperature range of 300–1500?K. All stationary points were calculated with the M06-2X/6-311++G(d,p) level of theory and identified for local minimum. The energetic parameters were refined at QCISD (T)/cc-pVTZ and CCSD (T)/cc-pVTZ levels of theory. Three channels were explored and a reaction of hydrogen abstraction from CH₂O by CH₃O₂ was identified as dominant channel which involves the formation of a prereactive complex in the entrance channel. The rate coefficient of the dominant channel was calculated with TST and TST/Eck and the Eckart tunnelling effect is only important over the lower temperature region. The calculated rate coefficient of the dominant channel has positive temperature dependence and agrees reasonably with the available literature data.     

Study on Adsorption States by Surface-Enhanced Raman Spectroscopy

Abstract

SERS has been used as a state-resolving probe to study the adsorption states. in the case of pyridine (Py) adsorbed on the Ag electrode surface, the equilibrium and transition between two adsorbed states, i.e., the perpendicular mode adsorbed through the nitrogen lone-pair electrons and the flat mode through the π electrons of the aromatic ring, were studied. It was found that in the low pyridine concentration or the initial stage of adsorption, the flat mode was favored. While the concentration became higher and the adsorption tended to equilibrium, the adsorbed molecules would transit to the perpendicular mode. The similar phenomenon was also observed when changing the applied electric potential and the pH value of the solution. In the case of the adsorption of Methylene Blue (MB) on the HNO₃-etched silver surface, the influence of Cl^? ions on the adsorption states of MB was investigated. It showed that MB molecules adsorbed on the silver surface tended to transform from the “lying-down” state to the “end-on” state while adding Cl^? ions.     

On the spurious eigenvalues for a concentric sphere in BIEM

In this paper, the null-field integral equation method is employed to study the occurring mechanism of spurious eigenvalues for a concentric sphere. By expanding the fundamental solution into degenerate kernels and expressing the boundary density in terms of spherical harmonics, all boundary integrals can be analytically determined. It is noted that our null-field integral formulation can locate the collocation point on the real boundary thanks to the degenerate kernel. In addition, the spurious eigenvalues are parasitized in the formulations while true eigensolutions are dependent on the boundary condition such as the Dirichlet or Neumann problem. By using the updating term and updating document of singular value decomposition (SVD) technique, true and spurious eigenvalues can be extracted out, respectively. Besides, true and spurious boundary eigenvectors are obtained in the right and left unitary vectors in the SVD structure of the influence matrices. This finding agrees with that of 2D cases.     

O-vacancy and surface on CeO2: A first-principles study

Atomic and electronic structures of CeO₂ (1 1 1), (1 1 0) and (1 0 0) surfaces are investigated using the first-principles density functional theory taking into account the on-site Coulomb interaction. Both the stoichiometric and O-deficient surfaces are examined in order to clarify the overall features. The CeO₂ (1 1 1) is found to be the most stable surface, followed by the (1 1 0) and (1 0 0) surfaces, consistent with experimental observations. Three surfaces exhibit different features of relaxation. Large relaxations are found at the (1 1 0) and (1 0 0) surfaces, while very small changes are observed at the (1 1 1) surface. It is found that the O-vacancy occurs more readily at the (1 1 0) surface as compared with the (1 1 1) surface. Furthermore, the formation energies of the O-vacancy in the surfaces are lower than that in the bulk. The energetically favorable O-vacancy locates in the second O-atomic layer for the (1 1 1) while at the surface layer for the (1 1 0). The excess electrons left with the removal of the O atom are distributed in the first two layers with certain (a considerable) fraction filling the Ce-4f states.     

Study on fast linear scanning for a new laser scanner

In the field of lidar system design, there is a need for laser scanners that offer fast linear scanning, are small size and have small a rotational inertia moment. Currently, laser scanners do not meet the above needs. A new laser scanner based on two amplified piezoelectric actuators is designed in this paper. The laser scanner has small size, high mechanical resonance frequencies and a small rotational inertia moment. The size of the mirror is 20 mm×15 mm. To achieve fast linear scanning performance, an open-loop controller is designed to compensate the hysteresis behavior and to restrain oscillations that are caused by the mechanical resonances of the scanner's mechanical structure. By comparing measured scanning waveforms, nonlinearities and scan line images between the uncontrolled and controlled scanner, it was found that the scanning linearity of linear scanning was improved The open-loop controlled laser scanner realizes linear scanning at 250 Hz with optical scan angle of ±12 mrad.     

Surface and catalytic properties of doped tin oxide nanoparticles

Mixed oxides composed of Zn-Sn, Ti-Sn and V-Sn were prepared by a co-precipitation method and evaluated as catalysts for methanol oxidation in an ambient fixed-bed reactor. Surface analysis by X-ray photoelectron spectroscopy (XPS) revealed an electronic interaction between dopant and Sn atoms in the oxide structure and showed the formation of surface states associated with the dopants. Oxygen vacancies were present on the Zn-doped oxide, and the oxidation of methanol to carbon oxides was favored. The Ti-doped oxide exhibited a favorable selectivity to dimethyl ether, related to the oxygen anions near Ti centers. Vanadium dopants not only dramatically increased the catalytic activity but also promoted the partial oxidation of methanol to formaldehyde. Results demonstrate that the bridging dopant-O-Sn bond acts as active sites and influences product distribution.     

Optical design for enhanced prism type fingerprint scanner image contrast with asymmetrical aspheric lens

The design of optical prism fingerprint scanner with aspheric lens is researched. We propose a modified structure for optical prism fingerprint scanner, which has an asymmetrical aspheric lens on the output plane. It is numerically shown under elliptic valley similar fingerprint model that the optical image qualities of such a scanner are better than the scanner with symmetrical aspheric lens. When the fingerprint range is 15 mm, the results show that the minimum image contrast is 0.49 for an optical prism with asymmetrical aspheric lens, much better than a symmetrical aspheric lens with 0.20. The relative illumination variation is from 0.62 to 1.00 for optical prism with asymmetrical aspheric lens, and for the symmetrical aspheric lens it is 0.35 to 1.00. We conclude that an optical prism with asymmetrical aspheric lens is better than an optical prism with symmetrical aspheric lens.     

Characteristics of Raman spectra of natural clinochlore at 200 degrees C and 0.95-7.70 GPa

Variation of crystal structure of natural clinochlore with pressure was investigated by the approach of diamond anvil cell (DAC) and in situ micro-Raman spectroscopic measurement at 200 degrees C and up to 7.7 GPa. The 481 and 786 cm(-1) peaks shift towards high-frequency linearly with increasing pressure at 200 degrees C. The linear relations between Raman shift (N, cm(-1)) and pressure (P, GPa) for the two peaks are: N = 11.136P+482.6 (R2 = 0.987 4) and N = 5.055P+785.7 (R2 = 0.983 7), respectively. The 865 cm(-1) peak arising from the stretching mode of the Si-O(nb) shifts slightly because of the strong repulsion between T cations at the tetrahedral sites and M cations at the octahedral sites in the TOT layer. Raman shift of 481 cm(-1) and 786 means the shortening of the length of M-O(br) and Si-CO(br) bonds since the peaks are contributed by the stretching mode of the M-O(br) and Si-O(br) respectively. No phase transition of clinochlore under the experimental condition was found. The results indicate that chlorite minerals may be stable at least at a depth of 80-90 km in the cold subduction zones, and the fluid derived from chlorite dehydration may be an important fact for earthquake occurrence in the subduction zones.