Benchmark Applications of Variations of Multireference Equation of Motion Coupled-Cluster Theory.

Abstract

In this work, several variations of the multireference equation of motion (MR-EOM) methodology are investigated for the calculation of excitation spectra. These variants of MR-EOM are characterized by the following aspects: (1) the operators included in the sequence of similarity transformations of the molecular electronic Hamiltonian, (2) whether permutational symmetries (i.e., hermitization, vertex symmetry) are imposed on the final elements of the similarity-transformed Hamiltonian, (3) the size of the manifold over which the similarity-transformed Hamiltonian is diagonalized, (4) whether the two-body cumulant is included in the expressions defining the amplitudes and the elements of the transformed Hamiltonian. The MR-EOM methods are benchmarked for the calculation of the excitation energies of a test set of organic molecules. With the availability of reliable benchmark data for this test set, it is possible to gauge the relative accuracy of these approaches. We also further examine a subset of the MR-EOM methods for the calculation of the excitation energies of some transition-metal complexes. These systems prove to be particularly difficult for single-reference coupled-cluster methods.