Brueckner doubles coupled cluster method with the polarizable continuum model of solvation

Abstract

We present the theory and implementation for computing the (free) energy and its analytical gradients with the Brueckner doubles (BD) coupled cluster method in solution, in combination with the polarizable continuum model of solvation (PCM). The complete model, called PTED, and an efficient approximation, called PTE, are introduced and tested with numerical examples. Implementation details are also discussed. A comparison with the coupled-cluster singles and doubles CCSD-PCM-PTED and CCSD-PCM-PTE schemes, which use Hartree-Fock (HF) orbitals, is presented. The results show that the two PTED approaches are mostly equivalent, while BD-PCM-PTE is shown to be superior to the corresponding CCSD scheme when the HF reference wave function is unstable. The BD-PCM-PTE scheme, whose computational cost is equivalent to gas phase BD, is therefore a promising approach to study molecular systems with complicated electronic structure in solution.