Natural orbitals as substitutes for optimized orbitals in complete active space wavefunctions

被引：68

作者：

Abrams, ML ^{[1
]}

Sherrill, CD ^{[1
]}

机构：

[1] Georgia Inst Technol, Sch Chem & Biochem, Ctr Computat Mol Sci & Technol, Atlanta, GA 30332 USA

来源：

CHEMICAL PHYSICS LETTERS | 2004年 / 395卷 / 4-6期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/j.cplett.2004.07.081

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：

Complete-active-space self-consistent-field (CASSCF) orbitals are computationally expensive and are sometimes difficult to converge. We assess complete-active-space configuration interaction (CASCI) in a basis of natural orbitals as a less expensive alternative to CASSCF. Natural orbitals are generated from various single-reference wavefunctions. The approach is applied to bond breaking in methyl fluoride and ethylene. With natural orbitals from correlated wavefunctions, CASCI parallels CASSCF potential curves, and coupled-cluster singles and doubles natural orbitals give nonparallelity errors of only 1-3 kcal mol(-1) even for a very large active space in methyl fluoride or double bond breaking in ethylene. (C) 2004 Published by Elsevier B.V.

引用

页码：227 / 232

页数：6

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