Second-order polarization propagator approximation with coupled-cluster singles and doubles amplitudes - SOPPA(CCSD): the polarizability and hyperpolarizability of

Abstract

A new modification of the second-order polarization propagator approximation (SOPPA) is presented. In the new method, called SOPPA(CCSD), all first-order Møller - Plesset doubles and second-order Møller - Plesset singles correlation coefficients are replaced with the corresponding coupled-cluster singles and doubles (CCSD) and amplitudes. This is in contrast to the earlier coupled-cluster polarization propagator approximation (CCSDPPA) in which only one of the doubles correlation coefficients was replaced in the unrelaxed second-order density matrix. The importance of this modification is investigated for the dipole polarizability, dipole oscillator strength sum rules and second hyperpolarizability of , which is known to be a difficult case for perturbative methods. The SOPPA(CCSD) values are compared with previous and new full CI results for the same basis sets.