A diagnostic for determining the quality of single-reference electron correlation methods

Abstract

It was recently proposed that the Euclidian norm of the t1 vector of the coupled-cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic T1 is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled-cluster energy. T1 is investigated for several different chemical systems which exhibit a range of multireference behavior and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T1 (i.e., >0.02) probably indicates the need for a multireference electron correlation procedure.