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Abstract

A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) in the multiexponential Jeziorski-Monkhorst formalism concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operators. If the reference space is a complete active space (CAS), the number of these amplitudes is larger than the number of singly and doubly excited determinants on which one may project the eigenequation, and one must impose additional conditions. The present work first defines a state-specific reference-independent operator (T) over tilde (m) which acting on the CAS component of the wave function vertical bar Psi(m)(0)> maximizes the overlap between (1 + (T) over tilde (m))vertical bar Psi(m)(0)> and the eigenvector of the CAS-SD (Singles and Doubles) Configuration Interaction (CI) matrix vertical bar Psi(m)(CAS-SD)> i. This operator may be used to generate approximate coefficients of the triples and quadruples, and a dressing of the CAS-SD CI matrix, according to the intermediate Hamiltonian formalism. The process may be iterated to convergence. As a refinement towards a strict coupled cluster formalism, one may exploit reference-independent amplitudes provided by (1 + (T) over tilde (m))vertical bar Psi(m)(0)> to define a reference-dependent operator (T) over cap (m) by fitting the eigenvector of the (dressed) CAS-SD CI matrix. The two variants, which are internally uncontracted, give rather similar results. The new MR-CC version has been tested on the ground state potential energy curves of 6 molecules (up to triple-bond breaking) and two excited states. The non-parallelism error with respect to the full-CI curves is of the order of 1 mE(h). Published by AIP Publishing.