Rank reduced coupled cluster theory. II. Equation-of-motion coupled-cluster singles and doubles.

Abstract

Equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) is a reliable and popular approach to the determination of electronic excitation energies. Recently, we have developed a rank-reduced CCSD (RR-CCSD) method that allows the ground-state coupled-cluster energy to be determined with low-rank cluster amplitudes. Here, we extend this approach to excited-state energies through a RR-EOM-CCSD method. We start from the EOM-CCSD energy functional and insert low-rank approximations to the doubles amplitudes. The result is an approximate EOM-CCSD method with only a quadratic number (in the molecular size) of free parameters in the wavefunction. Importantly, our formulation of RR-EOM-CCSD preserves the size intensivity of the excitation energy and size extensivity of the total energy. Numerical tests of the method suggest that accuracy on the order of 0.05-0.01 eV in the excitation energy is possible with 1% or less of the original number of wavefunction coefficients; accuracy of better than 0.01 eV can be achieved with about 4% or less of the free parameters. The amount of compression at a given accuracy level is expected to increase with the size of the molecule. The RR-EOM-CCSD method is a new path toward the efficient determination of accurate electronic excitation energies.