Rules on intrapair and interpair correlation energy for Cl, Cl?and MCl (M=H, Li, Na, K)

According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCl series compounds the value of Cl correlation energy contribution depends on the ionicity of MCl compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl^- anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions.     

Rules on intrapair and interpair correlation energy for Cl, Cl~(-) and MCI (M=H, Li, Na, K)

According to the calculation results of the intrapair and interpair correlation energy for the title systems, it has been found that the intrapair correlation energy of K shell of Cl is almost a constant and both the intrashell and intershell correlation energy of K and L shell changes little. It has also been found that in MCI series compounds the value of Cl correlation energy contribution depends on the ionicity of MCI compounds, i.e., the Cl correlation energy contribution increases with the increase of the ionic bond strength of the compound and this value is always less than the correlation energy of Cl" anion but always larger than that of Cl atom. These rules are helpful for the estimation of the correlation energy of ionic compounds and the energy changes of chemical reactions.     

On the structure of the Clifford algebra unitary group adapted states in the many‐electron correlation problem

An attempt has been made to understand the structure of the Clifford algebra unitary group adapted many‐particle states from the conventional symmetric group point of view. Emphasizing the symmetric group result that the consideration of the spin‐independent Hamiltonian matrix over the many‐particle configuration functions (CFs) entails a particular subspace of their spatial parts only, attention is confined entirely in this subspace. Question of adapting the functions therein to the unitary group subduction chain is then shown to bring out an interesting lead to the Clifford algebra unitary group approach (CAUGA) states, thus underlining the motive and the essential gains of the CAUGA formulation. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 607–614, 2000     

A nonlocal correlation energy density functional from a Coulomb hole model

A nonlocal correlation energy density functional based on the approximation of a model Coulomb hole is presented. The functional is constructed to describe both the homogeneous electron gas and nonuniform systems. In the nonuniform case, the functional satisfies all uniform, as well as most nonuniform, coordinate-scaling constraints. The numerical results for the homogeneous electron gas and for atoms He through Ar compare favorably with those of other correlation functionals. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 62: 603–616, 1997     

Electron correlation: the many-body problem at the heart of chemistry

The physical interactions among electrons and nuclei, responsible for the chemistry of atoms and molecules, is well described by quantum mechanics and chemistry is therefore fully described by the solutions of the Schr?dinger equation. In all but the simplest systems we must be content with approximate solutions, the principal difficulty being the treatment of the correlation between the motions of the many electrons, arising from their mutual repulsion. This article aims to provide a clear understanding of the physical concept of electron correlation and the modern methods used for its approximation. Using helium as a simple case study and beginning with an uncorrelated orbital picture of electronic motion, we first introduce Fermi correlation, arising from the symmetry requirements of the exact wave function, and then consider the Coulomb correlation arising from the mutual Coulomb repulsion between the electrons. Finally, we briefly discuss the general treatment of electron correlation in modern electronic-structure theory, focussing on the Hartree-Fock and coupled-cluster methods and addressing static and dynamical Coulomb correlation.     

On calculations of correlated wave functions with heavy configurational mixing

We discuss aspects of the theory and computation of wave functions and energies of discrete states of polyelectronic atoms that are represented in zero order by configurations with holes in subshells below the valence subshell. Both in zero order and in the remaining correlation components, such wave functions have particularities stemming from the state‐specific self‐consistent field and the heavy configurational mixing associated with near‐degeneracies and hole‐filling correlations. By referring to a variety of examples from small‐ and large‐scale calculations, it is noted that appropriate penetration into the many‐body problem can provide, in an economic and physically transparent way, reliable interpretations and semi‐ and fully quantitative understanding of issues related to states with inner holes and to cases of near‐degeneracies that result in strongly correlated wave functions. Whenever hole‐filling correlations are allowed, multiple correlations (i.e., beyond single‐ and double‐orbital substitutions in the single reference configuration) acquire increased importance relative to that in ordinary electronic structures. This is demonstrated via large‐scale multiconfigurational Hartree–Fock (MCHF) plus configuration interaction (CI) calculations on the Cl KL3s3p^{6 2}S discrete state, which is the lowest of its symmetry. The calculations incorporated correlations up to selected sextuple orbital excitations from the M shell. MCHF plus CI calculations at the level of quadruple orbital substitutions were also carried out for the Cl KL3s²3p^{5 2}P^o ground state and the excitation energy at this level of calculation was found to be 85,364 cm^?1, in excellent agreement with the experimental value of the fine‐structure‐weighted average, 85,385 cm^?1 (10.59 eV). Within the approximations of the calculation, the hole‐filling triple and quadruple orbital correlations, which, of course, are absent from the ²P^o state, contribute about 1 eV, which is significant. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Ab initio pseudopotential study of M2As− and M2Br+ (M = Cu,Ag, Au)

The equilibrium geometries and the vibration frequencies of M₂As⁻ and M₂Br⁺ (M = Cu, Ag, Au) are calculated at the Hartree–Fock (HF) and the second‐order Møller–Plesset (MP2) levels with pseudopotentials. The calculated results indicate that the species have a bent structure (C_2v). The electron correlation corrections on the geometrical structure are investigated at the MP2 level, the bond angles are reduced by 10°–20° for considered species. The electron correlation effects on the geometry of the Au₂As⁻ are studied particularly at MP2, MP3, MP4, CCSD and CCSD(T) levels. Comparing the species containing Ag and Au, the relativistic effects slightly short the bond lengths of the species. The bonding possibility of the Au₂As⁻ is predicted. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 38–43, 2000     

最大熵法分析寡聚核苷酸链内碰撞的荧光相关光谱

准确地由荧光相关光谱(FCS)的实验数据提取动力学信息一直是一个挑战. 本文对比了三种主要的方法: 依赖于模型的多指数函数法, 经验的拓展指数函数法和不依赖于模型的最大熵法. 多指数函数法的物理意义直接但在复杂体系中难以应用和解释. 拓展指数函数法简单易行但其物理意义含混不清. 最大熵法不依赖于具体的物理模型但拟合结果对实验噪音很敏感. 经研究我们发现一个好的选择是将最大熵法和多指数函数法结合在一起使用. 对寡聚核苷酸链内碰撞荧光相关光谱的研究发现, 在单链DNA中可以形成碱基对时, 有两个并行的链内碰撞反应. 以前的拓展指数函数法分析则不能提供这样的信息. 我们建议在荧光相关光谱研究中审慎地使用最大熵法.     

Enhanced second‐order treatment of electron pair correlation

Ab initio calculations have been performed for F₂, HCCH, H₂O, HF, (HF)₂, and (H₂O)₂, comparing certain electron pair correlation methods, or methods for doubly substituted configurations. In these model systems, the reweighting of substituted configurations that occurs beyond a second‐order perturbative treatment of electron correlation can be partly built into the second‐order analysis in a computationally trivial step. Specific means for doing this are explored, and they offer improvement in certain cases or else very little change. A consistent improvement in the correlation energy when judged against treatment with double substitution coupled cluster theory for the test species is obtained through one of these schemes. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 78: 226–236, 2000