Vibrational quasi-degenerate perturbation theory:: applications to fermi resonance in CO2, H2CO, and C6H6

被引：108

作者：

Yagi, Kiyoshi ^{[1
]}

Hirata, So ^{[2
]}

Hirao, Kimihiko ^{[3
]}

机构：

[1] Univ Tokyo, Sch Engn, Dept Appl Chem, Tokyo 1138656, Japan

[2] Univ Florida, Dept Chem, Quantum Theory Project, Gainesville, FL 32611 USA

[3] Japan Sci & Technol Agcy, CREST, Kawaguchi, Saitama 3320012, Japan

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2008年 / 10卷 / 13期

关键词：

D O I：

10.1039/b719093j

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A quasi-degenerate perturbation method with vibrational self-consistent field (VSCF) reference wavefunction is developed. It simultaneously accounts for strong anharmonic mode-mode coupling among a few states ( static correlation) by a configuration interaction theory and for weak coupling with a vast number of the other states ( dynamic correlation) by a perturbation theory. A general formula is derived based on the van Vleck perturbation theory. An algorithm that selects a compact set of the most important VSCF configurations which contribute to the static correlation is proposed and a scheme to limit the number of configurations considered for dynamic correlation is also implemented. This method reproduces the vibrational frequencies of CO2 and H2CO that are subject to the strongest anharmonic mode-mode coupling within 10 cm(-1) of vibrational configuration interaction results in a computational expense reduced by a factor of one to two orders of magnitude. The method also reproduces the infrared absorption of C6H6 in the CH stretching ( nu(12)) frequency region, in which combination tones nu(13)nu(16) and nu(2)nu(13)nu(18) appear on account of an intensity borrowing from nu(12) via the anharmonic coupling.

引用

页码：1781 / 1788

页数：8

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