Single particle orbitals for configuration interaction derived from quantum electrodynamics

By explicitly introducing degrees of freedom for the electromagnetic field into the Hamiltonian for an N-electron system, we propose a variational procedure leading to mean fields different from the Hartree-Fock field. We show that g-Hartree equations result if the electromagnetic field is assumed to be in a coherent state. Since the solutions of these equations, the g-Hartree orbitals, are derived from a variational ansatz more general than the Hartree-Fock functional, we expect them to be particularly suitable to furnish a single-particle basis set for fast converging configuration interaction (CI) calculations. We report configuration interaction studies on the water molecule in a double zeta basis set employing various single-particle basis set transformations for the construction of the configuration state functions and investigate the convergence behaviour of the CI expansion explicitly.

We find that the expansion in terms of g-Hartree orbitals receives substantially larger fractions of the total correlation energy in the case considered, if single excitations with respect to the mean field configuration are retained in the CI procedure.