Correlated frequency-dependent electronic first hyperpolarizability of small push¯pull conjugated chains

Denis Jacquemina,*, Benoît Champagne1,a and Christof Hättig2,b
a Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium
b Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

Chem. Phys. Lett. 319, 327-334 (2000).
(Received 17 February 1999; revised 27 September 1999)

The longitudinal component of the dynamic electronic first hyperpolarizability of ,-nitro,amino-polyacetylene oligomers containing a small number of unit cells has been computed at the Hartree-Fock, Møller-Plesset and coupled-cluster levels with different atomic basis sets. Using frequency-dependent coupled-cluster results, we have tested the efficiency of the additive and multiplicative corrections to approximate the frequency-dependent correlated values. The multiplicative approach provides frequency-dependent electronic first hyperpolarizability values that are within a few percent of the true correlated ones whereas the additive correction leads to L(-; 1, 2) too small by ~20%. It turns out that the MP2/6-31G procedure is a suitable approach to reach a semi-quantitative accuracy.

*Corresponding author. Research Assistant of the Belgian National Fund for Scientific Research. Fax: +32-81-724567; e-mail:

1Research Associate of the Belgian National Fund for Scientific Research.

2Present address: Forschungszentrum Karlsruhe, Institute of Nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germany.

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