The molecular structure and the analytical potential energy function of S2^- and S3^-

In this paper, the equilibrium geometry, harmonic frequency and dissociation energy of S2^- and S3^- have been calculated at QCISD/6-311＋＋G（3d2f） and B3P86/6-311＋＋G（3d2f） level. The S2^- ground state is of 2IIg, the S3^- ground state is of 2B1 and S3^- has a bent （C2v） structure with an angle of 115.65° The results are in good agreement with these reported in other literature. For S3^- ion, the vibration frequencies and the force constants have also been calculated. Base on the general principles of microscopic reversibility, the dissociation limits has been deduced. The Murrell-Sorbie potential energy function for S2^- has been derived according to the ab initio data through the least- squares fitting. The force constants and spectroscopic data for S2^- have been calculated, then compared with other theoretical data. The analytical potential energy function of S3^- have been obtained based on the many-body expansion theory. The structure and energy can correctly reappear on the potential surface.     

Ab initio calculation of force constants and equilibrium geometries

Force constants of the molecules HF, NH₃, CH₄ and BH₄ ^- have been calculated ab initio by the force method with a 73/3 + 1 gaussian lobe basis set. The results, including a former calculation on H₂O, agree well with experiment: the average relative error is 12 per cent for the diagonal force constants and the average absolute error is 0·06 mdyn/Å for the off-diagonal ones. The trends are also correctly reproduced. It is concluded that ab initio calculations of this accuracy can help to solve a number of spectroscopic problems. Force constants of BH₄ ^- have been determined from a combination of spectroscopic and ab initio information. Geometries have been obtained with little computing work and show good agreement with experiment.     

小变形原子核中的相干效应

本文考察了在转动的小变形核力场中运动的核子-核子对、核子-空穴对中的相干效应。计算了O¹⁸最低的偶宇称态0⁺,2⁺,4⁺和O¹⁶最低的奇宇称态0^-,1^-,2^-,3^-波函数;和壳模型经典方法计算出的结果作了比较,二者相当一致。得出的初步结论如下:核力主要是P₂力再加上一定成分具有相干性质的力。前者与转动的变形场等效。不但对于0⁺,2⁺,4⁺,3^-态,而且对于1^-,2^-态,附加的相干成分都很重要;它们的内部态混合组态是比较多的,粒子-粒子之间、或粒子-空穴之间的关联都比较显著。只有0^-态的内部态是纯组态。     

Electronic structure of clusters of A-15 compounds with radiation induced defects

The electronic structure of the clusters [V₃Si₄]^12-, [Nb₃Sn₄]^12- and [Mo₃Ge₄]^15- in crystalline V₃Si, Nb₃Sn, Mo₃Ge compounds is calculated by the Extended Hückel method. The influence of different types of radiation induced defects on the density of states at the Fermi level (the anti-site defects, the displacement of atoms in linear chains, the vacancy-interstitial type defects) is considered.     

The Vibrational Spectra of a Series of Simple Phosphorus/Chromium Polyoxoanions

The infrared and Raman spectra of polycrystalline samples of K₂HPCr₂O₁₀, Na₃PCr₃O₁₃.3H₂0, K₃PCr₄O₁₆ and (NH₄)₃PCr₄O₁₆ were recorded and discussed. A general vibrational assignment for the internal vibrations of these species is proposed.

The structural characteristics of an interesting series of simple polyoxoanions of the PCr_nO^3- _3n+4 type have been determined recently^1–7. These species are essentially built from a central PO₄ -tetrahedron which share a different number of corners with CrO₄ -tetrahedra.

As part of our present studies on different physico-chemical properties of polyoxoanions, we have investigated the vibrational spectra of crystalline species containing the following anions: HPCr₂O^2- ₁₀, PCr₃O^3- ₁₃ and PCr₄O^3- ₁₆.

As the three species have some common structural features, their vibrational spectra can be analyzed and compared in terms of these common building elements, i. e., terminal CrO₃ and PO groups and POCr bridges.

The interatomic distances in the above mentioned units are also very similar in all the anions and the Cr-O distances are similar to those found in the normal (triclinic) form of K₂Cr₂O₇ ⁸.     

The GVFT Force Constants for PO4 3-/Td/

The force constants for the tetrahedral PO₄ ^3- ion have been calculated on the basis of the general valence force field with the application of the Wilson FG matrix method^1,2.     

Force Constants,Coriolis Coupling Constants,and Mean Amplitudes of Vibration of InCl6 3-

Abstract

The general quadratic force constants, coriolis coupling constants and mean amplitudes of vibration have been evaluated for InCl₆ ^3- using recent vibrational data. The results are employed to study the trend of variation in the isoelectronic sequences e.g. InCl₆ ^3-, SnCl₆ ^2- and SbCl₆ ^?.

In the present communication we report the force constants, coriolis coupling constants and mean amplitudes of vibration for InCl₆ ^3- which have not been reported so far. The results are used to study the trend of variation of the molecular parameters in the isoelectronic sequence e.g. InCl₆ ^3-, SnCl₆ ^2- and SbCl₆ ^?. The fundamental frequencies of InCl₆ ^3-, employed in this computation, have been reported on the basis of octahedral symmetry, from infrared and Raman Spectral Studies¹.     

Influence of thermal and mechanical treatment and of water on structural phase transitions in CsHSO4

The influence of mechanical and thermal treatment on crystalline CsHSO₄ superionic protonic conductor has been studied by DSC, TGA, dilatometry, IR and Raman spectroscopies between 100 and 450 K. Grinding or pressing of CsHSO₄ destroys the (HSO₄)^- chains and induces a transition to a new phase containing cyclic (HSO^-₄)₂ dimers. The influence of dry and humid atmosphere on phase transitions is discussed. The structure of CsHSO₄ appears to be able to accomodate a large amount of defects such as S₂O^2-₇, SO^2-₄ or H₂O.     

Chemical-bond analysis of the nonlinear optical properties of the borate crystals LiB3O5, CsLiB6O10, and CsB3O5

The second-order nonlinear optical properties of practical borate crystals, LiB₃O₅, CsLiB₆O₁₀, and CsB₃O₅, which all contain the identical basic structural unit [the (B₃O₇)^5- group], have been quantitatively studied from the chemical-bond viewpoint. Differences in the nonlinear optical properties among these three borate crystals arise from the contributions of the different cations, i.e., the different interaction between the cation and the (B₃O₇)^5- anionic group. The chemical-bond method quantitatively expresses this important difference. At the same time, the current calculation also shows that the B₃O₇ group is a very important crystallographic frame in the crystalline borate solids; it offers different cations an excellent coordination environment. Received: 20 February 2001 / Accepted: 14 June 2001 / Published online: 30 August 2001     

Far-infrared optical properties of YVO4 single crystal

Near-normal incident infrared reflectivity spectra of a (001) YVO₄ single crystal have been measured at different temperatures in the frequency region between 100 and 6000 cm^-1. The reflectivity spectra are analyzed with the factorized form of the dielectric function, and the dielectric properties and optical conductivity of the YVO₄ crystal are obtained. From the TO/LO splitting, effective charges at different temperatures are calculated to study the ionicity of YVO₄. The internal modes of the VO₄^3- ion and the external modes of the Y(VO₄) lattice are compared with SiO₄^4- in zircon and with other rare-earth vanadates.     

On the intrinsic nature of the blue luminescence in CaWO4

Luminescence and thermoluminescence properties of nominally pure LiF and CaWO₄ crystals are compared with those of the crystalline system LiF/CaWO₄. Evidence is found which clearly indicates that from the various emission bands of CaWO₄ crystals only the blue one is of intrinsic nature. Luminescence decay measurements are reported. Within the spectral range of the blue tungstate band in LiF/CaWO₄ four different decay times are obtained. This result is interpreted as arising from WO^2-₄ luminescence centres with different environments in the LiF host.     

熔融Rb2ZnCl4的分子动力学模拟研究

采用在RbCl模拟和ZnCl₂模拟中选用的两体有效势，进行了晶态和熔融态Rb₂ZnCl₄的分子动力学模拟.模拟给出了Rb₂ZnCl₄ 6种径向分布函数，Zn-Cl和Rb-Cl间径向分布函数与新近的广延X射线吸收精细结构实验结果很好相符.在模拟产生的瞬态构型基础上进行了键序参数分析，研究了晶态和熔融态中的局部结构.模拟结果表明，Zn原子与其近邻Cl原子构成相当稳定的正四面体结构，并且熔融Rb_关键词：     

Paramagnetic defects in manganese-doped lead tungstate

In manganese-doped PbWO₄ crystals, low-intensity signals of triclinic clusters Mn⁴⁺-V _O and Fe³⁺-V _Pb have been revealed in addition to signals of Mn²⁺ tetragonal centers. The Mn⁴⁺-V _O cluster is formed by a Mn⁴⁺ ion in the W⁶⁺ position, which is associated with a vacancy of the nearest neighbor O^2?ion, and the Fe³⁺-V _Pb cluster consists of a Fe³⁺ ion substituting for Pb²⁺ with a local compensation of by a lead vacancy. It has been shown that, in PbWO₄: Mn, there is also a small amount of Mn⁴⁺ tetragonal centers located in the Pb²⁺ position with a nonlocal compensation of an excess charge.     

A multispectroscopic investigation of the electronic structure of luminescent,tetrahedrally coordinated vanadium-oxygen compounds: Case of YVO4

Photoelectron (XPS) and core ionization loss (CILS) spectra of YVO₄ have been measured and compared to our earlier appearance potential (APS) data on the same compound, literature data on X-ray emission of YVO₄, X-ray emission and absorption of Na₃VO₄, and the energy level diagram of molecular orbitals of the VO₄^3- cluster. Strong many-body effects, with participation of a 2p core hole on vanadium atoms, are found to lead to a drastic local perturbation of the outer molecular orbitals of the anionic cluster VO₄^3-, at the site of the excited vanadium atoms. Identification of the spectroscopic features in XPS on one hand and the edge spectroscopies CILS and APS on the other hand, enables determination of an empirical energy level diagram of excited configurations, which is different in different spectroscopies used. As a byproduct of our experiment, data on the excitation of oxygen (within the VO₄^3- cluster), yttrium (outside the VO₄^3- cluster), and carbon impurity are presented and discussed.     

Structural analysis of nonlinearities of Ca4ReO(BO3)3 (Re = La, Nd, Sm, Gd, Er, Y)

4 ReO(BO₃)₃ (CReOB, Re=La, Nd, Sm, Gd, Er, and Y) have been theoretically predicted. The d₁₁ tensor coefficient of CReOB is predicted to be -11 d₃₆(KDP), which is the largest d_ij tensor that has been found in borate crystals. From the structural characteristic of CReOB, we find the isolated BO₃ ^3- clusters play a dominant role in contributions to the total nonlinearity, and the largest d₁₁ tensor of CReOB-type crystals is also ascribed to these BO₃ ^3- clusters. We also find the NLO property of this family does not change dramatically for different rare-earth elements. The details of the calculation of CGdOB only are presented. Received: 3 March 1998/Accepted: 22 June 1998     

Crystal structure analysis of novel complex hydrides formed by the combination of LiBH4 and LiNH2

Combination of LiBH₄ and LiNH₂ by ball milling forms the series of novel complex hydrides Li₂BNH₆, Li₃BN₂H₈ and Li₄BN₃H₁₀, depending on the combination ratios. The crystal structure of Li₄BN₃H₁₀ analyzed by synchrotron X-raydiffraction measurements is determined to be a cubic system (space group: I2₁3) with the lattice constant of a=10.673(2)Å. It should be emphasized that Li₄BN₃H₁₀ is an ionic crystal which is composed of a lithium cation Li⁺ and two different kinds of the complex anion [BH₄]^- and [NH₂]^-. These anions are located in the vertex and face-center of the cubic sub-lattice, and the lithium cation Li⁺ in the interstitial site between the anions, respectively. The other series of complex hydrides, Li₂BNH₆ and Li₃BN₂H₈, are also predicted to possess similar structures composed of a lithium cation Li⁺ and two different kinds of the complex anion [BH₄]^- and [NH₂]^-.     

Electron affinities of the bromine oxides BrOn,n = 1-4

Bromine oxides are of significant interest due to their importance in atmospheric chemistry. Density functional theory (DFT) methods have been used in conjunction with a DZP++ (double-ζ plus polarization with diffuse functions) basis set to study the molecular geometries and total energies of BrOn and BrO^- _n (n = 1-4). The adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert) of the bromine oxide and the vertical detachment energy (VDE) of each anion are reported. Harmonic vibrational frequencies and zero point energies are also reported. Five different DFT methods were employed for comparison. Among these, the BHLYP method predicts the geometries and the vibrational frequencies in best agreement with available experimental data, while the the other methods do better in predicting the limited number of energetic quantities determined observationally. The predicted adiabatic electron affinities are 2.38 eV (BrO, experiment 2.35 eV), 2.36 eV (BrO₂), 3.35 eV (BrOO), 4.32 eV (BrO₃), 2.91 eV (BrOOO) and 5.28 eV (BrO₄). The electronic ground state of BrOO^- is a triplet (³A^") state. Predicted Br–;O bond distances range from 1.61 (BrO₃) to more than 2 Å for Br...O₂ for the neutral molecules; and from 1.61 Å for BrO^- to 1.82 Å for BrO^- to more than 2 Å for Br^-...O₃ among the anions. The BrOO isomer (C_s symmetry) is predicted to lie 17–18 kcal mol^-1 below the C_2v symmetry OBrO structure. The asymmetric ³A^" anion BrOO^- analogously lies below OBrO^-, in this case by 40–41 kcalmol_-1. BrOOO (C_s symmetry) is predicted to lie 42-45 kcalmol-1 below the symmetric C_3v BrO structure. Finally the asymmetric BrOOO- anion (C₁ symmetry) is predicted to lie 10-13kcal mol-1 below symmetric C_3v BrO^- ₃.     

Photoluminescence, optical absorption and XRD studies on X-ray irradiated terbium doped KBr crystals

This paper reports the optical absorption, photoluminescence (PL), XRD, SEM studies made on KBr:Tb³⁺ crystals. The integrated light intensity is enhanced by about two orders of magnitude as compared to the undoped samples in spite of some OH^- present in the samples. PL of these crystals exhibits characteristic Tb³⁺ emissions due to transitions from the ⁵D₃ to ⁵D₄ levels to various levels of the ⁷F septet on F-bleaching X-ray irradiated crystals Z₃ centers are observed. The bands observed in the emission spectra of Tb³⁺ doped KBr are found to be shifted to higher wavelength. The stokes-shift of KBr:Tb³⁺ is determined and it is found to have a large value. The XRD studies have been made to determine the crystalline structure of KBr and KBr:Tb³⁺ and also the Miller indices. The SEM studies made reveal the presence of microcrystalline structure.     

Vibrational spectra of (NH4)3ZnCl5

IR and Raman spectra of (NH₄)₃ZnCl₅ have been recorded. The observed spectra have been analysed on the basis of the vibrations of ZnCl ₄ ²⁻ and NH ₄ ⁺ ions. The appearance of multiple Raman bands indicates the presence of two different types of ammonium ions. The effect of anisotropic crystalline field over the ZnCl₄ and NH₄ tetrahedra is also discussed. The assignment of internal modes has been verified by the potential energy distribution calculations.     

Application of hyperspherical close-coupling method to antiproton collisions with muonic hydrogen

The cross sections for p^- + (Hμ^-)_1s (H = p, d, t) are calculated in the hyperspherical close-coupling method for collision energies below the (Hp^-)_n=4 threshold. The results show good convergence with respect to basis size. The formation cross section of (Hp^-)_n=2 is dominant and two orders of magnitude larger than that of (Hp^-)_n=1 below the (Hp^-)_n=3 threshold, while the (Hp^-)_n=3 formation cross-section exceeds that for (Hp^-)_n=2 formation above the (Hp^-)_n=3 threshold. Resonance parameters are also calculated below thresholds of (Hp^-)_n=2-4.