Can Coupled Cluster Singles and Doubles Be Approximated by a Valence Active Space Model?

Beran, G. J. O., Gwaltney, S. R., & Head-Gordon, M. (2002). Can Coupled Cluster Singles and Doubles Be Approximated by a Valence Active Space Model? Journal of Chemical Physics. 117, 3040-3048.

Abstract

A new, efficient approximation for coupled cluster singles and doubles (CCSD) is proposed in which a CCSD calculation is performed in a valence active space followed by a second-order perturbative correction to account for the inactive singles and doubles cluster amplitudes. This method, denoted VCCSD(SD), satisfactorily reproduces CCSD results in a variety of test cases, including spectroscopic constants of diatomic molecules, reaction energies, the Cope rearrangement, and other relative energies. Use of VCCSD alone is significantly less satisfactory. Formally, the O2V4 scaling of CCSD is reduced to o2v2V2, where o is the number of active occupied orbitals, v is the number of active virtual orbitals, and V is the total number of virtual orbitals. We also investigate the role of orbital optimizations and the appropriate choice of an active space in such methods.