A general nonorthogonal coupled electron pair approach for the evaluation of electron correlation contribution is presented in details. The self-consistent field for molecular interactions wave function is used as reference state for a multistructure valence bond (VB) calculation. The central idea of the method is the optimization of the virtual space of the VB wave function by means of a procedure very close to the independent electron pair approach (IEPA) scheme. All the orbitals employed are expanded in the basis set of their fragment so as to exclude the basis set superposition error (BSSE) in a priori fashion. As an example, the application to the study of the van der Waals complex He–CH4 is reported. The equilibrium geometry of the system occurs at a He–C distance of 3.6 Å , with the He atom pointing to the center of one of the faces of the CH4 molecule, with a well depth of 19 cm−1. The potential energy surface of the He–CH4 complex is used to determine the parameters of a potential model which is employed in close-coupling calculations of integral state-to-state cross sections for rotationally inelastic scattering of methane molecules with helium atoms. The predicted values are compared with the available experimental data.

Applications of a variational coupled-electron pair approach to the calculation of intermolecular interaction in the framework of the VB theory: Study of the van der Waals complex He-CH4 Source: JOURNAL OF CHEMICAL PHYSICS Volume: 113 Issue: 16 Pages: 6724-6735 Published: OCT 22 2000 Times Cited: 10

FAMULARI, ANTONINO;
2000

Abstract

A general nonorthogonal coupled electron pair approach for the evaluation of electron correlation contribution is presented in details. The self-consistent field for molecular interactions wave function is used as reference state for a multistructure valence bond (VB) calculation. The central idea of the method is the optimization of the virtual space of the VB wave function by means of a procedure very close to the independent electron pair approach (IEPA) scheme. All the orbitals employed are expanded in the basis set of their fragment so as to exclude the basis set superposition error (BSSE) in a priori fashion. As an example, the application to the study of the van der Waals complex He–CH4 is reported. The equilibrium geometry of the system occurs at a He–C distance of 3.6 Å , with the He atom pointing to the center of one of the faces of the CH4 molecule, with a well depth of 19 cm−1. The potential energy surface of the He–CH4 complex is used to determine the parameters of a potential model which is employed in close-coupling calculations of integral state-to-state cross sections for rotationally inelastic scattering of methane molecules with helium atoms. The predicted values are compared with the available experimental data.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11311/568848
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