A Coupled Cluster Theory Based on Quantum Electrodynamics

TL;DR

This paper develops a covariant coupled cluster method incorporating quantum electrodynamics effects, enabling accurate calculations of relativistic and QED corrections in many-electron systems, exemplified by noninteracting H2 molecules.

Contribution

It introduces a novel electrodynamical coupled cluster formalism based on QED and relativistic effects, extending traditional methods to include vacuum polarization and radiative corrections.

Findings

Ground state correlation energy includes relativistic and QED corrections.

Expressions derived for corrections to orbital and configuration energies.

Size-consistent formulation applicable to closed shell species.

Abstract

An electrodynamical coupled cluster (CC) methodology starting from a covariant formalism and an equal time approximation, and finally based on the Dirac-Fock picture of the electron and positron fields and Coulomb gauge, is given here. The formalism first leads to different physical interactions from the use of an exponential cluster operator for radiative effects. Lamb, Breit and hyperfine interactions are obtained. Next, relativistic many-body effects are determined using the matter cluster in a way familiar from the nonrelativistic CC. This step can be nontrivial. By allowing the matter cluster to deviate from its traditional excitation-only form, vacuum polarization effects are generated using the pair part of Coulomb interaction. The resulting ground state correlation energy includes both relativistic and QED corrections, the latter including contributions from Lamb, Breit, hyperfine and vacuum polarization effects. The many-electron part of the theory is explicitly formulated for closed shell species. The conservatism of the second step indicates that extensions to multireference and state-specific cases are possible. To illustrate the CC approach, expressions are derived for relativistic and QED corrections to the orbital energies, configuration energies and the ground state correlation energy in a minimal basis calculation on noninteracting H2 molecules. Size-consistency is maintained at every step. Because spinors of nonzero orbital angular momentum are absent, the spin-orbit interaction and Lamb shift corrections vanish in this example. However, one finds the kinetic energy correction, Darwin terms and corrections to the two-electron interaction in relativistic energy values through order mc2a4Z4, and Breit interaction energy and hyperfine splitting of levels as QED effects through the same order. Pair energies are explicitly shown through the lowest possible orders.