Density-functional theory (hyper)polarizabilities of push-pull π-conjugated systems:: Treatment of exact exchange and role of correlation

被引：123

作者：

Bulat, FA

Toro-Labbé, A

Champagne, B

Kirtman, B

Yang, WT ^{[1
]}

机构：

[1] Duke Univ, Dept Chem, Durham, NC 27708 USA

[2] Pontificia Univ Catolica Chile, Fac Quim, Lab Quim Teor Computat QTC, Santiago, Chile

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

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

来源：

JOURNAL OF CHEMICAL PHYSICS | 2005年 / 123卷 / 01期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1063/1.1926275

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：

The performance of the optimized effective potential procedure for exact exchange in calculating static electric-field response properties of push-pull pi-conjugated systems has been studied, with an emphasis on NO2-(CH = CH)(n)-NH2 chains. Good agreement with Hartree-Fock dipole moments and (hyper)polarizabilities is obtained; particularly noteworthy is the chain length dependence for beta/n. Thus, the problem that conventional density-functional theory functionals dramatically overestimate these properties is largely solved, although there remains a significant correlation contribution that cannot be accounted for with current correlation functionals. (c) 2005 American Institute of Physics.

引用

页数：7