AB INITIO STUDY OF LOW-LYING ELECTRONIC STATES OF THE AsH_2 RADICAL

The equilibrium geometries,excitation energies,force constants and vibrational frequencies for the low-ly- ing electronic states X ~2B_1,~2A_1,~2B_2 and ~2A_2 of the AsH_2 radical have been calculated at the MRSDCI level with a 3-21G~* basis set.Our calculated geometries,excitation enegies and vibional frequencies for the X ~2B_1 and ~2A_1 states are in good agreement with available experimental data.The electronic transition dipole mo- ments,oscillator strengths for the ~2A_1→X ~2B_1 and ~2A_2→X ~2B_1 transitions,radiative lifetimes for the ~2A_1 and ~2A_2 states are calculated based on the MRSDC^1 wavefunctions,predicting results in reasonable agreement with available experiment.

A POST-SCF STUDY ON THE EXCITED STATES OF MgH_2

The calculations on the ground state and two excited states3B2,BIB2 of MgH2 system are carried out by using (Second Order Configuration Interaction)method.For each state,the electronic structure and related properties are investigated,The vibration and localization analyses are also performed.The reasonable explanations of bending geometries for the excited states are given.

THEORETICAL STUDY ON THE EXCITED STATES AND STABILITIES OF B_3, B_3^- AND B_3^+

The geometries and vibrational frequencies of the ground and low-lying excited states for B_3, B_3^- and B_3^+ are determined with the energy gradient method using the polarized double-zeta(6-31G*) basis set. The stabilities for the states of B_3,B_3^- and B_3^+ have been investigated based on the vibrational analysis. The correlation energy obtained for each state is considered with the configuration interaction (CISD+Q) technique. B_3 and B_3^+ have stable equilateral triangle geometry, while B_3^- has stable equilateral triangle, isosceles triangle and linear geometries. The Jahn-Teller distortion for a ~3E' state of B_3^- in D_(3h) symmetry is also discussed.

A SCF-SOCI STUDY ON THE LOW-LYING STATES OF H_3^+

The ground state and three low-lying states of the H_3^+ are determined by SOCI(Second Order Configuration Interaction) calculations. The results indicate that the ~3Σ_u^+ state of H_3^+ 3 is a bound state, but ~1A_1 and ~3A_1 states are not stable, each of them will dissociate into H_2^+ and H atom. The SOCI energy -1.1144065au at an equidistant nuclear separation of 1.296A is in good agreement with the lowest value reported so far.

CAS-MCSCF Study on the Ground State of the Ditungsten Molecule(W_2)

Complete active space multiconfiguration self-consisten-field (CAS-MCSCF)calculations are carried out on the ground stae() of W_2. The spectroscopic properties(Re=2.078A. De=4.224eV and ωe=304.3cm-1) and the poential energy curve of the state are reported. The calculations predict the W-W bond order of 5.02.

AN SCF-CI STUDY OF HIGHLY EXCITED VIBRATIONAL STATES OF BENT TRIATOMIC MOLECULES AND ITS APPLICATION TO O_(3)

A self-consistent-field—configuration interaction(SCF-CI)procedure of studying highly excited vibrational states of bent triatomic molecules is suggested and its application to O_3 is investigated.

THE APPLICATION OF MICROELECTRODE TO THE STUDY OF MULTISTEP ELECTRODE PROCESSES UNDER STEADY STATE CONDITIONS PART I EE MECHANISM

Under steady-state conditions, the general currents of EE reactions at disk,hemispherical and spherical microelectrodes are derived.From these equations, some electrode reaction parameters can be very simply obtained.

Review: Hu Houxuan, "Xia and the Tu State in the Oracle Inscriptions: A Consideration" Gudai Chengbang Shi Yanjiu (Studies on Ancient City States) Renmin Press, 1989, Pp. 340-353.

This article verified that the Tu state mentioned in the oracle inscriptions was the Xia people after the Xia Dynasty had been conquered by Tang, the first king of the Shang Dynasty m c.a. 16th century B.C. The state of Xia, which originated from Yu, was entitled "Xia Hou"; its king was hence called "Xia Hou Di" (Emperor of Xia Hou), e.g."Xia Hou Di Qi". The Xia people, together with the Yin (Shang) people, and the Zhou people, were the so-called "people of San Dai" (Three Dynasties). As mentioned in "Lunyu, Bayi", they founded the states, with the Xia people being associated with the pine, the Yin people with the cypress, and the Zhou people with the chestnut.

STUDIES ON SOLID STATE REACTIONS OF COORDINATION COMPOUNDS(LXⅡ)Solid state synthesis and crystal structure of the complex ICu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)CIJ·0.5CS_2

[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15cm^(-1),F(000)=1855,R=0.052, R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis. torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)), Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .

MRSDCI STUDIES OF LOW-LYING ELECTRONIC STATES OF THE N_2F^+ MOLECULE

Ab initio electronic structure calculations are reported for low-lying electronic states,X ~1Σ^+and A ~1Π of the N_2F^+ molecule.Geometric parameters for the ground state X ~1Σ^+ are predicted by means of mul- tireference single and double excitation configuration interaction(MRSDCI)calculations with a double zeta plus polarization(DZ+P)basis set.Vertical excitation energy for these two electronic states is determined using MRSDCI/DZ+P calculations at the ground state equilibrium geometry.The oscillator strength for the X^1Σ+→ A ~1Π transition and the radiative lifetime for the A^1Π state are calculated based on the MRSDCI wavefunc- tions.

Studies on Some Basic Physical Problems in Macromolecular Condensed State

Macromolecular condensed state involves crystalline state and non-crystalline state of long-chain synthetic and naturally occurring molecules. The noncrystalline state may be a polymeric fluid, a rubbery elastic semi-solid or a rigid glass.

^(13)C NMR and structural study of solid state naphthol-1 and naphthol-2 arylazo-derivatives

Solid state ^(13)C NMR spectra of a series of naphthol-1 and naphthol-2-arylazo--deriva- tives were studied and compared with respective results in solutions.Signals of carbon nuclei of naphthalene ring were assigned.Tautomeric forms of compounds were determined.It was shown that 4-(p-NO_2C_6H_4)-azonaphthol-1 and 1-(p-NO_2C_6H_4)-azonaphthol-2 in solid state existed ex- clusively in quinohydrazone form.The other two compounds——1-(C_6F_5)-azonaphthol-2 and 2-(p- CH_3C_6H_4)-azonaphthol-1 in solid state were not found in the form of individual tautomeric mixtures but in respective tautomeric equilibrium form.Thus,during transition from liquid to solid state, the tautomeric equilibrium was practically unchanged.In solid state it was found that rotation around aryl-N bond was hindered in the time scale of NMR spectroscopy.

Variational transition state theory study of the reactions Li+HF and Li+HCl on the BO potential energy surfaces

Variational transition state theory is used to study the kinetics of the reactions Li+HF and Li+HCl on the BO potential energy surfaces, fitted to ab initio values by Lagana et al. The saddle point, the location of generalized transition state and other kinetic features on the bottleneck of the po- tential energy surface are obtained. We point out that the location of generalized transition state tends to the direction in which the two atoms with larger reduced mass separate off. It can be determined whether a potential energy surface is accurate or not by a fine analysis of its bottleneck region and a comparison of kinetic calculation with experimental result. This is helpful for building a more accurate potential energy surface.

Studies on the solid state reactions of coordination conpounds——XLⅤⅢ.The effect of KSCN on the thermal decomposition of cobalt(Ⅲ)-ammine complexes

The evolved gaseous analysis (EGA),infrared spectra,and XRD have been applied to the study of solid state reactions of KSCN with five cobalt(Ⅲ)-ammine complexes:[Co- (NH_3)_5N_3]Cl_2,[Co(NH_3)_5(NO_2)]Cl_2,[Co(NH_3)_5(H_2O)]Cl_3,[Co(NH_3)_5Cl]Cl_2,and [Co(NH_3)_6]Cl_3 in a hydrogen atmosphere.It is found that the existence of KSCN shifts the thermal decom- position of these complexes to a lower temperature.The corresponding peak temperatures are near 140℃.The effect of KSCN is discussed and kinetic parameters of deammine reactions are calculated.

A First-Principles Study on the Vibrational and Electronic Properties of Zr-C MXenes

Within the framework of density functional theory calculations,the structural,vibrational,and electronic properties of Zr_(n )C_(n-1)(n=2,3,and 4)and their functionalized MXenes have been investigated.We find that the most stable configurations for Zr-C MXene are the ones that the terminal groups F,O,and OH locate on the common hollow site of the superficial Zr layer and its adjacent C layer.F and OH-terminated Zr_3C_(2 )and Zr_4C_(3 )have small imaginary acoustic phonon branches aroundΓpoint while the others have no negative phonon modes.The pristine MXenes(Zr_2C,Zr_3C_(2 )and Zr_4C_3)are all metallic with large DOS contributed by the Zr atom at the Fermi energy.When functionalized by F,O and OH,new hybridization states appear and the DOS at the Fermi level are reduced.Moreover,we find that their metallic characteristic increases with an increase in n.For(Zr_(n )C_(n-1))O_2,Zr_2CO_(2 )is a semiconductor,Zr_3C_2O_(2 )is a semimetal,and Zr_4C_3O_(2 )becomes a metal.

Electrical,Magnetic and Catalytic Investigations on Some Manganite Perovskites Prepared by Combustion Method

AMnO3 （A=Sr, Sm and Nd） manganites with perovskite structure, prepared by combustion method were characterized by X-ray diffraction （XRD）, infra-red spectroscopy, Brunauer-Emmett-Teller （BET） surface area analyzer and scanning electron microscopy （SEM）. The solid state and spectroscopic studies such as electrical resistivity, magnetic susceptibility, electron spin resonance （ESR） and diffuse reflectance spectroscopy were carried out and attempted to correlate with the catalytic activities of the compounds. To evaluate the catalytic activity, a model reaction of CO oxidation over these compounds was undertaken. An attempt was made to understand the effect of A-site change by different metal cations in the manganite perovskites on solid state and catalytic properties.