压缩氦原子团簇Hen（n＝3，4，5）排斥势及其多体展开分量计算

 采用Lowdin方法计算了处于压缩状态的氦原子团簇He_n（n＝3，4，5）的排斥势及其多体展开分量。发现随原子数目或压缩度增大，多体展开式的收敛性变差。多体展开式中两体势分量、四体势分量为正值，三体势分量和五体势分量为负值。因此，在进行近似处理时，两体近似法计算的排斥势偏高。经三体修正后的排斥势必然偏低。该计算结果与最新的实验结果定性符合。发现四体势和五体势分量对高密度氦状态方程仍然具有重要贡献。     

高压固氩物态方程的量子理论计算

基于第一性原理,运用ab initio超分子单、双(三)重激发耦合簇理论(CCSD(T))和aug-cc-pVQZ基矢,精确计算了fcc晶体固氩在最近邻原子间距R=0.20~0.39nm时的两体、三体和四体结合能,零点振动能及物态方程。结果表明:固氩的多体势对结合能的贡献在高压区域是一正负交叉级数;零点振动能占多体相互总能的比例较小,但不可忽略;在高压区域,只考虑两体势时对固氩的压缩特性表现过硬,加入三体势后与实验结果在60GPa内完全吻合,考虑到四体势后对整个实验区间0~114GPa内做出令人满意的描述,且在压强达到114GPa时与实验值相差约3GPa,吻合程度达到97%。最后,通过与密度泛函理论的局域密度近似和广义梯度近似方法比较发现,泛函理论(DFT)只有在50~114GPa范围内与实验值符合较好,不如本研究所采用方法适用的压强范围宽。     

嵌入原子法计算金属钚中点缺陷的能量

钚因放射性衰变而出现老化效应.钚中点缺陷的性质和行为是理解钚老化效应的一个基础和前提.运用分子动力学模拟技术,计算了金属钚中点缺陷和点缺陷团簇的形成能和结合能.其中钚-钚、钚-氦和氦-氦相互作用势分别采用嵌入原子多体势、Morse对势和Lennard-Jones对势.计算结果表明,单个自间隙原子易以〈100〉哑铃状形态存在;间隙氦原子在理想晶格的八面体间隙位置相对较为稳定;氦原子与空位的结合能较大,在钚的自辐照过程中两者易于结合并形成氦-空位团簇;氦-空位团簇的形成能随氦原子数的增加而增大,当氦与空位的数     

MRCI方法研究CSe(X1Σ+)自由基的光谱常数和分子常数

采用内收缩多参考组态相互作用方法在0.08—2.5 nm的核间距范围内计算了CSe(X¹Σ⁺)自由基的势能曲线.为确保势能曲线的计算精度,C原子使用较大的相关一致基aug-cc-pV5Z,Se原子使用最大的相对论赝势基aug-cc-pV5Z-pp.对CSe(X¹Σ⁺)自由基的势能曲线进行了拟合,并进行了同位素识别,得到了该自由基6个主要同位素分子(¹²C^{74< 关键词： 同位素识别 势能曲线 光谱常数 分子常数}     

相对论离子与氦二聚体碰撞电离的理论研究

基于对称程函近似,从理论角度研究了相对论离子与氦二聚体碰撞双电离的直接碎裂通道:由入射离子与两个原子的作用造成的双电离。从不同的近似角度出发,建立了两个理论模型,第一个模型将氦二聚体的两个原子看做一个整体,而另外一个模型完全忽略了两个氦原子之间的相互作用。模型的数值计算结果表明,总截面与氦二聚体的空间取向有很强的依赖关系,当氦二聚体与入射离子束流平行时,总截面达到最大值,在垂直时为最小值。进一步研究发现,模型一的结果在氦二聚体核间距较小时更为合理,核间距较大时,模型二更为精确。     

基于第一性原理的固氦零点振动能的量子理论计算

基于第一性原理,运用原子团簇理论和Hartree-Fock Self-Consistent-Field从头算法计算了高压固氦hcp结构在平衡位置r=1.75-2.6附近的原子相互作用能,并使用1stOpt软件拟合出固氦的零点振动频率,得到零点振动能、Gruneisen系数及零点振动压强,最后与实验值做了比较.结果表明:固氦晶体在其各自平衡位置附近的运动可近似为简谐振动;固氦晶体的零点振动频率随着摩尔体积的增大而减小;零点振动能占多体相互总能的比例超过5%,已不可忽略,其比例随摩尔体积的增加而增大;零点振动能随原子间距和摩尔体积的增大而减小;Gruneisen系数随着摩尔体积的增大而增大,并始终处于1和2之间;零点振动引起的压强与实验值曲线趋势完全一致,但比实验值稍小,零点振动压强对总压强的贡献随着摩尔体积的增大由8%增大到50%左右,由此引起的零点振动压强值的贡献越来越大.     

VH2+分子离子的结构与势能函数

本文从VH2 分子离子基态的电子状态及其离解极限出发,采用B3PW91的方法,对V原子采用SVP基组,对H原子采用6-311 G基组优化出VH2 (X3A2)分子离子稳定构型的平衡核间距Re=0 .1631 nm,∠HVH =112 .3858°,同时计算出振动频率,并使用多体项展式理论方法,导出了基态VH2 分子离子的分析势能函数,该势能表面准确地再现了VH2 (C2v)平衡结构,然后根据势能函数等值图讨论了反应势能面的静态特征,并利用杂化轨道理论解释了VH2 分子离子的结构.     

氦原子1snd(n=4—11)组态下1D—3D谱项分裂值的计算

利用多体微扰理论(MBPT)计算了氦原子1snd(n=4—11)组态的１Ｄ—^３Ｄ谱项分裂值.基于两种不同的模型分别计算Rayleigh-Shrdinger微扰展开式中仅含束缚态的部分和包含连续态的部分.对于束缚态，较严格地通过自洽迭代求解Hartree方程构造零级近似波函数，并利用积分处理方法对无穷项求和中的余项给出了近似算法.而对于连续态波函数，则采用简化的氢原子势模型.按照Rayleigh-Shrdinger微扰展开方法，将Rydberg态的微扰论修正计算至三级.计算表明，二级和三级微扰对谱项分裂的贡献主要来自于束缚态求和部分.单态-三重态精细结构分裂的计算结果与两组实验结果基本符合. 关键词： 氦原子 Rydberg态 多体微扰 组态波函数 能级分裂     

PdPbH分子的结构与势能函数

在相对论有效原子实势近似下,用密度泛函理论的B3LYP方法,对钯和铅采用LANL2DZ基函数,氢原子采用6-311 G**全电子基函数,对PdPb、PdPbH分子的结构进行优化.计算表明:PdPb分子的基态为X1∑ ,键长RPdPb=0.24536 nm,离解后Pd原子处于基态(单重态)而Pb原子处于激发态(单重态),离解能为3.107686 eV,引入开关函数拟合得到Murrell-Sorbie势能函数;PdPbH分子最稳态为Cs构型,电子组态为X2A′,键长RPdPb=0.2547 nm,RPdh=0.15919 nm,键角∠PbPdH=64.7856°,离解能De=4.79 eV.由微观过程的可逆性原理分析了分子的可能离解极限,并用多体项展开式理论方法分别导出基态PdPb和PdPbH分子的势能函数,其等值势能面图准确的再现了PdPb和PdPbH分子的结构特征和离解能,由此讨论了Pd Pb H分子反应的势能面静态特征.     

基于第一性原理的固氦零点振动能的量子理论计算

基于第一性原理,运用原子团簇理论和Hartree-Fock Self-Consistent-Field从头算法计算了高压固氦hcp结构在平衡位置r=1.75-2.6Å附近的原子相互作用能,并使用1stOpt软件拟合出固氦的零点振动频率,得到零点振动能、Gruneisen系数及零点振动压强,最后与实验值做了比较.结果表明：固氦晶体在其各自平衡位置附近的运动可近似为简谐振动;固氦晶体的零点振动频率随着摩尔体积的增大而减小;零点振动能占多体相互总能的比例超过5%,已不可忽略,其比例随摩尔体积的增加而增大;零点振动能随原子间距和摩尔体积的增大而减小;Gruneisen系数随着摩尔体积的增大而增大,并始终处于1和2之间;零点振动引起的压强与实验值曲线趋势完全一致,但比实验值稍小,零点振动压强对总压强的贡献随着摩尔体积的增大由8%增大到50%左右,由此引起的零点振动压强值的贡献越来越大.     

On the multipole structure of exchange dispersion energy in the interaction of two helium atoms

The exchange dispersion energy for the interaction of two helium atoms is expressed as a sum of multipole components. In contrast to the analogous expansion for the dispersion energy the derived series converges very slowly and the rate of convergence does not improve with an increasing interatomic distance. Numerical calculations show that at the van der Waals minimum the first term of the series, referred to as dipole-dipole exchange energy, represents merely 17 per cent of the exchange dispersion energy. Moreover, even the inclusion of dipole-quadrupole and quadrupole-quadrupole terms can account for only half of the total exchange dispersion interaction. The above difficulty can be avoided by expanding the dispersion pair function in terms of ionic type or explicitly correlated functions.     

四体相互作用对固氦压缩特性的贡献

运用从头计算自洽场方法和原子团簇理论计算了高压下固氦原子间的四体势分量.计算结果表明四体分量对结合能的贡献为正；随着压缩度增大四体势的贡献比例变大.采用两体、三体、四体势和Aziz吸引势计算固氦零温状态方程并与实验测量相比较，结果表明两体势对固氦的压缩性贡献了过多的正效应，加入三体分量的修正，仅在低于10GPa时理论值与实验值相符很好，但考虑了四体势修正后能将理论值与实验值符合程度提高到 27GPa. 关键词： 状态方程 固氦 四体势 从头计算     

部分电离稠密氦等离子体物态方程的自洽变分计算

稠密氦在高温高压下将会发生电离, 电离能会因为原子、离子以及电子之间的相互作用而降低. 考虑He，He⁺，He²⁺，e之间的相互作用, 通过粒子化学势平衡得到非理想的电离平衡方程，用自洽流体变分过程对方程求解, 进而对自由能求导获得体系的热力学状态参量. 模型计算结果与已有的实验和理论计算相一致. 用此模型预测密度10^-3—10^0.3 g/cm³和温度4—7 eV范围的物态方程, 获得了压力在500　GPa以内的理论数据. 计算表明粒子间的非理想相互作用引起的电离能降低是出现压致电离现象的主要原因，在高温高密度物态方程的计算中必须考虑粒子间非理想相互作用对电离能修正的影响. 关键词： 氦 物态方程 部分电离等离子体 自洽变分     

Excitation of helium atoms in collisions with plasma electrons in an electric field

The rate constants are evaluated for excitation of helium atoms in metastable states by electron impact if ionized helium is located in an external electric field and is supported by it, such that a typical electron energy is small compared to the atomic excitation energy. Under these conditions, atomic excitation is determined both by the electron traveling in the space of electron energies toward the excitation threshold and by the subsequent atomic excitation, which is a self-consistent process because it leads to a sharp decrease in the energy distribution function of electrons, which in turn determines the excitation rate. The excitation rate constant is calculated for the regimes of low and high electron densities, and in the last case, it is small compared to the equilibrium rate constant where the Maxwell distribution function is realized including its tail. Quenching of metastable atomic states by electron impact results in excitation of higher excited states, rather than transition to the ground electron state for the electric field strengths under consideration. Therefore, at restricted electron number densities, the rate of emission of resonant photons of the wavelength 58 nm, which results from the transition from the 2¹ P state of the helium atom to the ground state, is close to the excitation rate of metastable atomic states. The efficiency of atomic excitation in ionized helium, i.e., the part of energy of an electric field injected in ionized helium that is spent on atomic excitation, is evaluated. The results exhibit the importance of electron kinetics for an ionized gas located in an electric field.     

Equation of state of metallic helium

The effective ion-ion interaction, free energy, pressure, and electric resistance of metallic liquid helium have been calculated in wide density and temperature ranges using perturbation theory in the electron-ion interaction potential. In the case of conduction electrons, the exchange interaction has been taken into account in the random-phase approximation and correlations have been taken into account in the local-field approximation. The solid-sphere model has been used for the nuclear subsystem. The diameter of these spheres is the only parameter of this theory. The diameter and density of the system at which the transition of helium from the singly ionized to doubly ionized state occurs have been estimated by analyzing the pair effective interaction between helium atoms. The case of doubly ionized helium atoms has been considered. Terms up to the third order of perturbation theory have been taken into account in the numerical calculations. The contribution of the third-order term is significant in all cases. The electric resistance and its temperature dependence for metallic helium are characteristic of simple divalent metals in the liquid state. The thermodynamic parameters—temperature and pressure densities-are within the ranges characteristic of the central regions of giant planets. This makes it possible to assume the existence of helium in the metallic state within the solar system.     

Microscopic theory of multiple scattering for open-shell nuclei

We consider the scattering of a distinguishable projectile from a nucleus assuming that the underlying interaction Hamiltonian is a sum of two-body potentials. We show that the effective interaction of the projectile with the nucleus in a truncated nuclear model space can be calculated as a linked-cluster expansion. The rules for evaluating this expansion are given in terms of the nucleon-nucleon and projectile-nucleon potentials and the exact eigenstates of the (effective) shell-model interaction. The shell-model interaction is required to be an energy-independent, Hermitian potential; its expression in terms of the underlying two-body potential is given by folded diagrams. The terms in the expansion of the effective projectile-nucleus interaction must also contain folded diagrams but, unlike the shell-model potential, these are energy-dependent in order to describe the singularities associated with the crossing of the scattering thresholds as the projectile energy is varied. Once the effective interaction is known, elastic and inelastic scatterings may be evaluated numerically by solving a finite-dimensional coupled-channel equation.     

Thermal Shift Calculations (Ⅰ): The Theory for Thermal Shift of Crystal Field Spectra of Rare Earth or Transition Metal Ions

The thermal shift of crystal field spectra of rare earth or transition metalions includes four contributions of different characteristics. In this paper we develop a theory of calculating all those contributions in detail. The contributions to thermal shift consist of that of thermal expansion and those of electron-phonon interaction. The thermal shift caused by thermal expansion is interpreted and calculated by making use of theory of pressure-induced spectral shift. The contribution of phonons of optical branches is given by using single frequency model. The contributions of phonons of acoustic branches include two terms, which are derived by taking into account contributions of all the Γγ in electron-phonon interaction.The theoretical form'ulas for parameters in the most important term are given.     

Bound State Effects in Quantum Transport Theory

A quantum kinetical equation for the one-particle density operator for inhomogeneous multi component non-ideal gases is derived taking into account retardation effects and external fields. It is shown that the interactions give rise to additional contributions to the quantities in the transport equation. In some terms (e.g., internal energy, pressure, effective external force) the interaction effects are strong in the presence of bound states and yield contributions of the order exp (—E₁₀/kT) where E₁₀ is the ground state energy of bound pairs of particles. Other terms (e.g. friction forces) are rather insensitive with respect to the presence of bound states. An interpretation of these effects in terms of the mass action law is given using the principle of equivalence between bound states and particles.     

一种适用于原子团簇的多体展开新方案: 以氮团簇为例

多体展开方法虽然已经广泛地用于估算弱相互作用体系的能量,但是其并不适用于计算共价团簇和金属团簇的能量. 本文提出了一种适用于计算共价体系能量的相互作用多体展开(IMBE)方法. 在相互作用多体展开方法中,体系的能量表示为孤立原子的能量及该原子与其他周围原子间相互作用的和. 首先将该方法应用于计算氮团簇的能量,且多体展开截断至四体项. 结果表明：与传统的多体展开方法相比,相互作用多体展开方法可以显著地降低能量误差. 另外,以密度泛函理论计算结果为参考,相互作用多体展开方法估算能量的误差不依赖于体系的大小和结构,说明相互作用多体展开方法比较适合用于估算共价相互作用大体系的能量.