The coherent-state transformation in quantum electrodynamics coupled cluster theory

Abstract: We analyse the coherent-state (CS) transformation in quantum electrodynamics coupled cluster (QED-CC) theory from the perspective of its non-vanishing commutator with the polaritonic cluster operator. Specifically, we show that a QED Hartree-Fock (QED-HF) reference state parametrized by the CS-transformation leads to a QED-CC Lagrangian formally determined by CS-representations of polaritonic Hamiltonian, polaritonic cluster and polaritonic deexcitation operators. This observation augments the original formulation of QED-CC theory where the CS-representation is restricted to the polaritonic Hamiltonian. We consequently find a renormalization of both QED-CC correlation energy and QED-CC ground state induced by the CS-transformation, which depends on the mean-field expectation value of the molecular dipole operator and therefore breaks origin invariance for charged systems. Electronic contributions to correlation energy and QED-CC ground state are renormalized by CS-transformed mixed excitation and deexcitation operators. In contrast, the CS-transformed single-photon excitation affects only the QED-CC ground state but not directly the correlation energy. The fully CS-transformed QED-CC ansatz is well approximated by the original QED-CC formulation for large cavity frequencies leading to small renormalization corrections. However, it exhibits a divergent zero-frequency limit absent in the original QED-CC ansatz for molecules with a non-vanishing molecular dipole moment in agreement with the asymptotic behaviour of the CS-parametrized QED-HF reference state.