Collect. Czech. Chem. Commun. 2008, 73, 1415-1436

A Comparison of Møller-Plesset and Coupled Cluster Linear Response Theory Methods for the Calculation of Dipole Oscillator Strength Sum Rules and C6 Dispersion Coefficients

Ivana Paidarováa,* and Stephan P. A. Sauerb

a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 182 23 Prague 8, Czech Republic
b Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark


Four correlated linear response theory methods - the second order polarization propagator approximation (SOPPA), the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes, SOPPA(CCSD), the CC2 and coupled cluster singles doubles (CCSD) linear response theory - were used to determine the dipole oscillator strength sum rules of the hydrogen halides HX (with X = F, Cl, Br and I) and the C6 dispersion coefficient for all pairs of interacting HX molecules via numerical integration of the Casimir-Polder formula. The dependence of the polarizabilities, their frequency dependence and the C6 coefficients on the level of correlation and the dependence of the C6 coefficients on the two intramolecular bond lengths were studied.

Keywords: Van der Waals complexes; Dispersion coefficients; Dipole oscillator strength sum rules; Coupled clusters linear response method; Møller-Plesset perturbation theory linear response method.

References: 151 live references.