A NEW VARIATIONAL COUPLED-ELECTRON PAIR APPROACH TO THE INTERMOLECULAR INTERACTION CALCULATION IN THE FRAMEWORK OF THE VALENCE BOND THEORY : THE CASE OF THE WATER DIMER SYSTEM
A NEW VARIATIONAL COUPLED-ELECTRON PAIR APPROACH TO THE INTERMOLECULAR INTERACTION CALCULATION IN THE FRAMEWORK OF THE VALENCE BOND THEORY : THE CASE OF THE WATER DIMER SYSTEM
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价键理论框架下计算分子间相互作用的一种新的变分耦合电子对方法：以水二聚体系统为例
DOI：
10.1063/1.479925
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发表时间：
1999
影响因子：
4.4
通讯作者：
M. Raimondi
中科院分区：
文献类型：
--
作者：
Roberto Specchio;A. Famulari;M. Sironi;M. Raimondi
本文提出了一种基于虚轨道中间优化的非正交耦合电子对方法。由此产生的程序，类似于独立的电子对近似方案，开发的价键（VB）理论的框架中，重叠的影响直接考虑在内。从分子相互作用波函数的自洽场出发，确定了分子间相关效应的最佳非正交虚轨道。这些都是用在上下文中的一般从头变分多结构VB波函数由双激发所产生的同时单激发本地化的每个单体。基组叠加误差被排除在一个先验的方式和几何松弛效应自然考虑。作为应用实例，确定了水二聚体体系的平衡结构和结合能。平衡氧-氧距离导致...
A general nonorthogonal coupled-electron pair approach based on the intermediate optimization of virtual orbitals is presented. The resulting procedure, similar to the independent electron pair approximation scheme, is developed in the framework of the valence bond (VB) theory, where the effect of the overlap is directly taken into account. Nonorthogonal virtual orbitals optimal for intermolecular correlation effects were determined starting from the self-consistent field for molecular interaction wave function. These were used in the context of a general ab initio variational multistructure VB wave function consisting of double excitations arising from simultaneous single excitations localized on each monomer. The basis set superposition error is excluded in an a priori fashion and geometry relaxation effects are naturally taken into account. As an application example, the equilibrium structure and binding energy of the water dimer system were determined. The equilibrium oxygen–oxygen distance results to...
影响因子：
4.4
作者：
Huisken, F;Kaloudis, M;Kulcke, A
通讯作者：
Kulcke, A