Dipole polarizability and second hyperpolarizability of difluoroacetylene: Basis set dependence and electron correlation effects

Issue title: Computational aspects of electric polarizability calculations: Atoms, Molecules and clusters, Part I

Article type: Research Article

Authors: Medveď, Miroslav^{a; **} | Champagne, Benoît^{a; *} | Noga, Jozef^{b; c} | Perpète, Eric A.^a

Affiliations: [a] Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles 61, B-5000 Namur, Belgium | [b] Institute of Inorganic Chemistry, Slovak Academy of Science, Dúbravská cesta 9, SK-84536 Bratislava, Slovak Republic | [c] Department of Physical and Theoretical Chemistry, Faculty of Science, Comenius University, SK-84215, Bratislava, Slovak Republic

Correspondence: [*] Corresponding author. Tel.: +32 81 724554; Fax: +32 81 724567; E-mail: [email protected].

Note: [**] Permanent address: Department of Chemistry, Matej Bel University, Tajovského 40, SK-97400 Banská Bystrica, Slovak Republic.

Abstract: Ab initio calculations of the static dipole polarizability and the static and dynamic second hyperpolarizabilities, including the electron correlation effects via the standard Coupled Cluster method with single and double excitations (CCSD) and non-iterative triple excitations (CCSD(T)) as well as the vibrational motion (nuclear relaxation) effects by means of the Finite Field method formulated by Kirtman and co-workers, have been carried out for difluoroacetylene (C2F2). The basis set dependence of the geometry parameters and molecular properties using various types of basis sets (ANO-L, POL, HyPOL, aug-cc-pVTZ) is analysed. A particular attention is devoted to the evaluation of the electron correlation effects on the vibrational contributions to the molecular properties.

Keywords: polarizability, second hyperpolarizability, basis set dependence, electron correlation, coupled cluster method, nuclear relaxation, infinite frequency approximation, finite field method

DOI: 10.3233/JCM-2004-4303

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 4, no. 3, pp. 251-265, 2004