Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo, Norway
Lehrstuhl für Theoretische Chemie, Institut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany and Institut für Nanotechnologie, Forschungszentrum Karlsruhe, P.O. Box 3640, D-76021 Karlsruhe, Germany
Institut für Nanotechnologie, Forschungszentrum Karlsruhe, P.O. Box 3640, D-76021 Karlsruhe, Germany
J. Chem. Phys. 123, 094303 (2005).
(Received 31 May 2005; accepted 5 July 2005; published online 6 September 2005)
The frequency-dependent electric field-induced second harmonic generation (ESHG) second hyperpolarizabilities gamma of neon, argon, and krypton are calculated using the approximate coupled cluster triples model CC3. Systematic basis set investigations are carried out to establish basis set limits, and scalar relativistic effects are accounted for by direct perturbation theory. To estimate higher-order correlation effects, full configuration-interaction results are used to benchmark the accuracy of CC3. The best theoretical estimates obtained thereby for the static second hyperpolarizabilities γo are 107.4, 1159, and 2589 a.u. for neon, argon, and krypton, respectively. These values as well as the results for the dispersion curve of the parallel component γ(parallel to) agree well with the latest experimental values from electric field-induced second harmonic generation. In addition, the dispersion of the perpendicular component γ⊥ and the hyperpolarizability ratios γ(parallel to)/γ⊥ has been studied for the first time on a consistently correlated ab initio level. The analysis of the results indicates that, in particular for neon and krypton, the presently available experimental values are flawed. (C) 2005 American Institute of Physics.
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