ELECTRON CORRELATION-EFFECTS IN HYPERPOLARIZABILITIES OF P-NITROANILINE

被引:274
作者
SIM, F
CHIN, S
DUPUIS, M
RICE, JE
机构
[1] IBM CORP,DEPT MLMAMS428,NEIGHBORHOOD RD,KINGSTON,NY 12401
[2] IBM CORP,ALMADEN RES CTR,DIV RES,SAN JOSE,CA 95120
关键词
D O I
10.1021/j100108a010
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 importance of including electron correlation effects in the determination of the equilibrium structure and hyperpolarizabilities of p-nitroaniline is investigated. Second-order perturbation theory gives static hyperpolarizabilities which are 88% to 100% larger than those obtained without electron correlation. These values are scaled by a self-consistent field frequency-dependent contribution for comparison with experimental measurements. Despite the large increase in beta(-2omega;omega,omega) from electron correlation, the theoretical result is still 3 times smaller than the experimental value obtained in solution. This difference is discussed. The finite field perturbation approach for calculating hyperpolarizabilities is discussed, and we outline a generalization of a previous method based on the solution of simultaneous equations.
引用
收藏
页码:1158 / 1163
页数:6
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