The effect of intermolecular interactions on the electric properties of helium and argon. Part I: Ab initio calculation of the interaction induced polarizability and hyperpolarizability of He2 and Ar2

Christof Hättig, Helena Larsen, Jeppe Olsen, Poul Jørgensen
Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

Henrik Koch
Department of Chemistry, University of Odense, DK-5230 Odense M, Denmark

Berta Fernández
Department of Physical Chemistry, Faculty of Chemistry, University of Santiago de Compostela, E-15706 Santiago de Compostela, Spain

Antonio Rizzo
Istituto di Chimica Quantistica ed Energetica Moleculare del Consiglio Nazionale delle Ricerche, I-56126 Pisa, Italy

J. Chem. Phys. 111, 10099-10107 (1999).
(Received 21 July 1999; accepted 16 September 1999)

The frequency-dependent interaction induced polarizabilities and second hyperpolarizabilities are calculated for He2 at the coupled cluster singles and doubles and full configuration interaction levels and for Ar2 at the coupled cluster singles and doubles level. The frequency-dependence is approximated by a power series to second-order in the frequency arguments using Cauchy moments and hyperpolarizability dispersion coefficients. Using large correlation consistent basis sets, results close to the basis set limit are obtained. The computed curves for the interaction induced (hyper-) polarizabilities are tabulated for a range of internuclear distances. The data are employed in a companion paper to make for the first time a direct comparison between the experimentally determined pressure dependence of an ESHG hyperpolarizability and ab initio calculated hyperpolarizability second virial coefficients.

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