Towards Near-Exact Solutions of Molecular Electronic Structure: Full Coupled-Cluster Reduction with a Second-Order Perturbative Correction.

Abstract

We introduce a new augmented adaptation of the recently developed full coupled-cluster reduction (FCCR) with a second-order perturbative correction, abbreviated as FCCR(2). FCCR is a selected coupled-cluster expansion aimed at optimally reducing the excitation manifold and commutator expansions for high-rank excitations for obtaining accurate solutions of the electronic Schödinger equation in a size-extensive manner. The present FCCR(2) enables estimating the residual correlation of FCCR by the second-order perturbative correction E(2) from the complementary space of the FCCR projection manifold. The linear relationship between E(2) and the energy of FCCR(2) allows accurate estimates of near-exact energies for a wide variety of molecules with strong electron correlation. The potential of the method is demonstrated using challenging cases, the ground-state electronic energy of the benzene molecule in equilibrium and stretched geometries, and the isomerization energy of the transition metal complex [Cu(NH3)]2O22+.