Molecular Physics, 104 , 2306-2316 (2006)

Tatiana Korona, Michal Przybytek, and Bogumil Jeziorski

Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland

Time-independent coupled cluster theory of the polarization propagator. Implementation and application of the singles and doubles model to dynamic polarizabilities and van der Waals constants

Abstract

Recently proposed time-independent coupled cluster theory of the polarization propagator [R. Moszynski, P. S. Zuchowski, and B. Jeziorski, Collect. Czech. Chem. Commun. 70, 1109, 2005] has been implemented at the single and double excitations (CCSD) level. The performance of the new approach was investigated by carrying out calculations of static and dynamic electric dipole polarizabilities for various molecules and by making a comparison with values obtained from other ab initio methods, including the full configuration interaction (FCI) technique. Our results show that the polarizabilities computed with the new approach are in a good agreement with the time-dependent CCSD and (when available) FCI values. The isotropic C₆ dispersion coefficients for several benchmark van der Waals complexes, e.g. dimers of helium, argon, water, and benzene, are also reported. They compare very well with existing experimental and best theoretical data. The new propagator, implemented already in the MOLPRO package, is computationally somewhat less demanding than the propagator of the time-dependent coupled cluster theory, and can be considered as an alternative to the latter in applications to large molecules and in studies of their interactions.

Dedicated to Prof. A. J. Sadlej on the occasion of his 65th birthday

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