Properties of nonadiabatic couplings and the generalized Born-Oppenheimer approximation

被引：99

作者：

Kendrick, BK

Mead, CA

Truhlar, DG

机构：

[1] Los Alamos Natl Lab, Div Theoret, Los Alamos, NM 87545 USA

[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[3] Univ Minnesota, Inst Supercomp, Minneapolis, MN 55455 USA

来源：

CHEMICAL PHYSICS | 2002年 / 277卷 / 01期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/S0301-0104(02)00281-1

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：

We present a new analysis of the nonadiabatic coupling terms in the coupled equations for nuclear motion wave functions when the Born-Oppenheimer (BO) representation is used for the electronic wave function. The new analysis leads to a criterion for truncating the series and neglecting terms in the coupled equations of motion. We show that in general the nonremovable part of the coupling is of the same magnitude as the removable part, except near intersections of the adiabatic states. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：31 / 41

页数：11

共 42 条

[1] An optimal adiabatic-to-diabatic transformation of the 1 2A′ and 2 2A′ states of H3 [J].