Multi‐state multi‐reference Møller–Plesset second‐order perturbation theory for molecular calculations

This work presents multi‐state multi‐reference Møller–Plesset second‐order perturbation theory as a variant of multi‐reference perturbation theory to treat electron correlation in molecules. An effective Hamiltonian is constructed from the first‐order wave operator to treat several strongly interacting electronic states simultaneously. The wave operator is obtained by solving the generalized Bloch equation within the first‐order interaction space using a multi‐partitioning of the Hamiltonian based on multi‐reference Møller–Plesset second‐order perturbation theory. The corresponding zeroth‐order Hamiltonians are nondiagonal. To reduce the computational effort that arises from the nondiagonal generalized Fock operator, a selection procedure is used that divides the configurations of the first‐order interaction space into two sets based on the strength of the interaction with the reference space. In the weaker interacting set, only the projected diagonal part of the zeroth‐order Hamiltonian is taken into account. The justification of the approach is demonstrated in two examples: the mixing of valence Rydberg states in ethylene, and the avoided crossing of neutral and ionic potential curves in LiF. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Relativistic perturbation theory of molecular structure

Summary The recently developed relativistic double perturbation theory is extended to handle relativistic changes of molecular structure more easily. This is achieved by simple coordinate scalings. Accurate higher order mixed perturbation energies for H ₂ ⁺ are calculated. The relativistic changes of bond energy,DE, of bond length,R _e , and especially of force constant,k, and of anharmonicity,a, are large, up to 100%·(Z/c)². The dominant contributions tok anda are due to the indirect change of the nonrelativistick anda connected with the relativistic change of bond length. Accordingly the relativistic changes obey Badger's and Gordy's rules (–RDEk).Dedicated to Prof. Klaus Ruedenberg in appreciation of his fundamental contributions to both formal theory and physical explanations in quantum chemistry     

Theoretical DFT and experimental Raman and NMR studies on thiophene, 3-methylthiophene and selenophene

The results of extended MO calculations using density functional theory (DFT) approximation supported by experimental Raman, ¹H and ¹³C NMR studies on thiophene are reported. Raman spectra of liquid thiophene were re-examined and the performance of a hybrid B3PW91 density functional was compared with the ab initio restricted Hartree–Fock (RHF) method. With the basis sets of the 6-311++G^** quality, the DFT calculated bond lengths, dipole moments and harmonic vibrations were predicted in a very good agreement with available experimental data.

Additionally, the results on thiophene were extended by calculations on 3-methylthiophene and selenophene. In this case, a significant change in geometry and charge distribution in thiophene ring due to a methyl group substituent or replacement of sulphur by selene atom was observed.

A linear correlation between the predicted harmonic vibrational frequencies (scaled using SQM method) and experimental ones for thiophene, selenophene and 3-methylthiophene was shown. The theoretically calculated spectra have satisfactorily reproduced the available experimental spectra for thiophene and selenophene.     

A theoretical determination of the electronic spectrum of formaldehyde

Summary The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the 0-0 transition for the valence¹A₁( *) state is calculated to appear near 7.9 eV, close to the (n _y 3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition.     

Ising-like field theory

A field theory model onR ² in which the basic fields are Ising spins instead of Gaussian spins is examined. Using statistical mechanics techniques we discuss the ultraviolet and the infrared problems. In particular we discuss a technique yielding the asymptotic expansion in of the ground state energy, as 0, without using the cluster expansion.Supported in part by Consiglio Nazionale delle Ricerche.     

van der Waals corrections to density functional theory calculations: Methane,ethane, ethylene,benzene, formaldehyde,ammonia, water,PBE, and CPMD

Parameters are developed for a practical application of the empirical van der Waals (vdW) correction infrastructure available in the CPMD density functional theory (DFT) code. The binding energy, geometry, and potential energy surface (PES) are examined for methane, ethane, ethylene, formaldehyde, ammonia, three benzene dimer geometries, and three benzene–water geometries. The vdW corrected results compare favorably with MP2 and CCSD(T) calculations near the complete basis set limits, and with experimental results where they are available.     

Mg-Cu-La三元非晶合金形成范围的热力学预测

基于分析有利于合金非晶化的热力学因素，从非晶形成的热力学观点出发，综合应用Miedema理论和Toop模型，并考虑纯金属在不同温度下的自由能，在此基础上提出了一种定量预测三元非晶合金形成范围的方法：通过比较晶态的自由能和相应非晶态的自由能来确定成分范围．用该方法计算Mg—Cu—La三元合金系的非晶形成范围，并与已有的实验数据进行比较，发现二者符合得较好．该方法对于定量预测二元及三元甚至是多元合金系非晶形成范围将有一定的指导意义．     

光致聚合材料收缩对谱面全息存储的影响

为了分析光致聚合材料记录的谱面全息图在再现过程中发生"擦除"现象,将谱面全息图看作由不同角谱的物光与参考光在光致聚合材料内形成的不同倾斜角度的光栅总和.使用二波耦合理论分析全息图像再现时,由于光致聚合材料发生形体收缩,不同倾斜程度的光栅发生不同程度的变形,产生不同程度的布拉格失配带来的衍射效率变化.理论分析表明,材料收缩越严重,全息图再现质量越差.实验证明了理论分析的正确性,并表明使用无收缩光致聚合材料可以消除这种"擦除"现象.     

脑信息特征的评价分类方法

对脑信息处理的能力特征量和总体偏离度特征量进行了确定性评价分类.在分类数上,提出了common分类法,以一般人的特征作为分类基准,在common两边展开,以确定分类数.在分类边界上,提出了根据特征量的正态分布确定分类边界的方法.若特征量分布不是正态分布,则采用了博克斯和考克斯变换将其变为正态分布,最终得到能力特征量和总体偏离度特征量的分类规则.由于人的行为是脑信息处理在宏观上的表现,所以其研究成果可直接用来评价人的能力和行为特征.     

基于GIS的中国松树萎蔫病发生的适应性评价

松材线虫在中国被认为是最具有破坏性和威胁性的外来入侵生物种之一.松材线虫潜在的区域扩散不论是从环境保护的角度还是从经济损失的角度都会对森林生态系统健康的服务功能和美学价值产生很大的影响.在中国存在很多的松材线虫容易感染的寄主植物,其中日本黑松和马尾松已经被证明是最容易感染的树种.媒介昆虫松墨天牛(Monochamus alternatus Hope),是松材线虫病在中国传播的主要媒介昆虫.这种天牛主要分布在河北及河北南部的大部分省份,其大范围存在使松材线虫病在中国更大区域的传播和扩散成为可能.中国大部分地区的温度和积温都适合松树萎蔫病病原线虫和媒介昆虫的大面积发生.利用GIS对传媒昆虫、寄主树木、病原线虫以及气候等空间信息处理和分析,得出松材线虫病在中国有着极大扩散和传播可能,其中广东部分地区、广西和福建部分地区为松树萎蔫病理论上发生最为严重的区域;安徽、江苏、浙江、上海、湖南、湖北、贵州、四川、河南和山东部分地区为松树萎蔫病理论上发生的适宜区.科学的预防和严格的地区间检疫等措施对目前防止松材线虫更大范围内传播很有必要.