Extensive regularization of the coupled cluster methods based on the generating functional formalism: application to gas-phase benchmarks and to the SN2 reaction of CHCl3 and OH- in water.
The recently introduced energy expansion based on the use of generating functional (GF) [K. Kowalski and P. D. Fan, J. Chem. Phys. 130, 084112 (2009)] provides a way of constructing size-consistent noniterative coupled cluster (CC) corrections in terms of moments of the CC equations. To take advantage of this expansion in a strongly interacting regime, the regularization of the cluster amplitudes is required in order to counteract the effect of excessive growth of the norm of the CC wave function. Although proven to be efficient, the previously discussed form of the regularization does not lead to rigorously size-consistent corrections. In this paper we address the issue of size-consistent regularization of the GF expansion by redefining the equations for the cluster amplitudes. The performance and basic features of proposed methodology are illustrated on several gas-phase benchmark systems. Moreover, the regularized GF approaches are combined with quantum mechanical molecular mechanics module and applied to describe the S(N)2 reaction of CHCl(3) and OH(-) in aqueous solution.
Kowalski
Karol
K
William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, K8-91 Battelle, P.O. Box 999, Richland, Washington 99352, USA. karol.kowalski@pnl.gov
Valiev
Marat
M