Dynamical Mean-Field Theory for Quantum Chemistry

TL;DR

This paper extends dynamical mean-field theory from bulk materials to molecules, enabling efficient approximation of their electronic structure with competitive accuracy for energies and spectra.

Contribution

It introduces a novel application of dynamical mean-field theory to finite molecular systems, bridging a gap between condensed matter and quantum chemistry methods.

Findings

Ground state energies competitive with leading quantum chemical methods

Accurate approximations to excitation spectra

Effective for small hydrogen clusters at various interatomic distances

Abstract

The dynamical mean-field concept of approximating an unsolvable many-body problem in terms of the solution of an auxiliary quantum impurity problem, introduced to study bulk materials with a continuous energy spectrum, is here extended to molecules, i.e., finite systems with a discrete energy spectrum. The application to small clusters of hydrogen atoms yields ground state energies which are competitive with leading quantum chemical approaches at intermediate and large interatomic distances as well as good approximations to the excitation spectrum.