Coupled cluster theory based on quantum electrodynamics: Physical aspects of closed shell and multi-reference open shell methods

Abstract

Electrodynamical coupled cluster (CC) methodologies have been formulated employing standard QED Hamiltonian that is written in Coulomb gauge while using the DF and the MCDF pictures of the matter field for closed-shell and open-shell cases respectively. The general methodology employs a radiative cluster, pure matter clusters and their pair modifications, and a number state distribution of photons in thermal equilibrium. The closed-shell treatment relies on the customary CC approach. For open shells, QED and electron correlation through CC are treated on the same footing. An averaging over the radiation state is done to generate Lamb, Breit and hyperfine interactions from the radiative cluster. Because of the thermal distribution, it leaves a residual transverse interaction that may modify the static correlation in open shells. Dynamical correlation effects are determined next by using the exponential matter cluster in traditional ways of single- and multi-reference CC. When the matter cluster is extended to include de-excitations to negative-energy levels, vacuum polarization effects are generated from the pair part of Coulomb interaction. The dynamical correlation energy includes relativistic corrections as well as QED contributions, namely, Lamb, Breit, hyperfine and pair energy. This work has three novelties: (i) QED interactions (Lamb, Breit and hyperfine) are obtained from a single procedure based on the radiative cluster; (ii) pair energy is determined from an extended matter cluster formalism; and (iii) additional correlation energy can be had from radiative effects and pair terms, while the option for higher order pair energy in high-Z atoms is kept open. The open-shell formalism has one more novelty in finding an additional static correlation in certain cases when the radiation is not isotropic.