Pseudo linear-dependence and long-range interaction effects on the polarizability and hyperpolarizabilities of stereoregular polymers

被引：14

作者：

Champagne, B

Jacquemin, D

Gu, J

Gu, FL

Aoki, Y

Kirtman, B

Bishop, DM

机构：

[1] Fac Univ Notre Dame Paix, Lab Chim Theor Appl, B-5000 Namur, Belgium

[2] Univ Ottawa, Dept Chem, Ottawa, ON K1N 6N5, Canada

[3] Hiroshima Univ, Grad Sch Sci, Dept Chem, Higashihiroshima 7398526, Japan

[4] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

CHEMICAL PHYSICS LETTERS | 2003年 / 373卷 / 5-6期

基金：

日本学术振兴会; 加拿大自然科学与工程研究理事会;

关键词：

D O I：

10.1016/S0009-2614(03)00631-6

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：

Effects of pseudo linear-dependence and long-range interactions in calculating (hyper)polarizabilities of several stereoregular polymers are addressed. Long-range Coulomb interactions in the TDHF equations can be accurately determined using a multipole expansion. Although these terms are small they ensure fast convergence with the size of the medium-range region and are often compulsory for SCF convergence. We find that (hyper)polarizabilities can be significantly underestimated by eliminating columns of the transformation matrix associated with small eigenvalues in the procedure to remove pseudo linear-dependencies. Finally, exchange interactions converge rapidly with the size of the short-range region. (C) 2003 Elsevier Science B.V. All rights reserved.

引用

页码：539 / 549

页数：11

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