Electron correlation effects in hyperpolarizabilities of p-nitroaniline

Fiona Sim, Steven Chin, Michel Dupuis, Julia E. Rice

Research output: Contribution to journalArticle

255 Citations (Scopus)

Abstract

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 β(-2ω;ω,ω) 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.

Original languageEnglish
Pages (from-to)1158-1163
Number of pages6
JournalJournal of Physical Chemistry
Volume97
Issue number6
Publication statusPublished - 1993

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Electron correlations
simultaneous equations
electrons
self consistent fields
perturbation theory
perturbation
4-nitroaniline

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Electron correlation effects in hyperpolarizabilities of p-nitroaniline. / Sim, Fiona; Chin, Steven; Dupuis, Michel; Rice, Julia E.

In: Journal of Physical Chemistry, Vol. 97, No. 6, 1993, p. 1158-1163.

Research output: Contribution to journalArticle

Sim, Fiona ; Chin, Steven ; Dupuis, Michel ; Rice, Julia E. / Electron correlation effects in hyperpolarizabilities of p-nitroaniline. In: Journal of Physical Chemistry. 1993 ; Vol. 97, No. 6. pp. 1158-1163.
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