TDMP2 calculation of dynamic multipole polarizabilities and dispersion coefficients of the halogen anions F-, Cl-, Br-, and I-

Christof Hättiga and Bernd Artur Heß
Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstr. 12, D-53115 Bonn, Germany
aAlso at: Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

J. Chem. Phys. 108, 3863-3870 (1998).
(Received 27 October 1997; accepted 4 December 1997)

A systematic ab initio study of the dynamic multipole polarizabilities of the halogen anions F-, Cl-, Br- and I- is presented. The effects of electron correlation are included for the static as well as for the frequency-dependent polarizabilities using time-dependent second-order Møller-Plesset perturbation theory. Large one-particle basis sets, optimized for polarizabilities, are used to obtain results near the MP2 basis set limit. For the anions Br- and I- also scalar relativistic effects are accounted for by means of the spin-free no-pair Hamiltonian Hsf1+. For the static dipole polarizabilities of the anions F- and Cl- we find good agreement with recent correlated ab initio calculations, but for the higher multipole polarizabilities and for the anions Br- and I- the discrepancies relative to previous calculations and empirical estimates are large. The effects of electron correlation on the polarizabilities of these anions are in general extremely large, while relativistic effects are in all four investigated halogen anions only of minor importance. The dynamic polarizabilities of the halogen anions are combined with previously calculated dynamic polarizabilities for rare gas atoms and the molecules CO and N2 to obtain isotropic and anisotropic dispersion coefficients for the corresponding van der Waals complexes.

View Article:     PDF   (access restricted to domain

Related articles:

Back to the list of Publications by the Quantum Chemistry (Hättig) Group