Many-body calculations of molecular electric polarizabilities in asymptotically complete basis sets

Ruben Monten (1) , Balazs Hajgato (1) , Michael S. Deleuze (2)

1 Theoretical Chemistry and Molecular Modelling
2 Theoretical Chemistry

The static dipole polarizabilities of Ne, CO, N2, F2, HF, H2O, HCN, and C2H2 (acetylene) have been determined close to the Full-CI limit along with an asymptotically complete basis set (CBS), according to the principles of a Focal Point Analysis. In this purpose we employed the results of Finite Field calculations up to the level of Coupled Cluster theory including Single, Double, Triple, Quadruple and perturbative Pentuple excitations [CCSDTQ(P)], in conjunction with suited extrapolations of energies obtained using augmented and doubly-augmented Dunning's correlation consistent polarized valence basis sets of improving quality. The polarizability characteristics of C2H4 (ethylene) and C2H6 (ethane) have been determined on the same grounds at the CCSDTQ level in the CBS limit. Comparison is made with results obtained using lower levels in electronic correlation, or taking into account the relaxation of the molecular structure due to an adiabatic polarization process. Vibrational corrections to electronic polarizabilities have been empirically estimated according to Born-Oppenheimer Molecular Dynamical simulations employing Density Functional Theory. Confrontation with experiment ultimately indicates relative accuracies of the order of 1 to 2 %.

Mots clés: Physical Sciences

Domaines: Matière Condensée [cond-mat]

Ruben Monten, Balazs Hajgato, Michael S. Deleuze. Many-body calculations of molecular electric polarizabilities in asymptotically complete basis sets. Molecular Physics, 2011, 109 (19), pp.2317-2339. ⟨10.1080/00268976.2011.579580⟩. ⟨hal-00743833⟩