Dynamical Mean Field Theory for Diatomic Molecules and the Exact Double Counting

Abstract

Dynamical mean field theory (DMFT) combined with the local density approximation (LDA) is widely used in solids to predict properties of correlated systems. In this paper, its application to one of the simplest strongly correlated systems, the hydrogen molecule H$_2$, is demonstrated to develop a parameter-free LDA+DMFT framework. We propose a method to calculate the exact intersection of LDA and DMFT that leads to highly accurate subtraction of the doubly counted correlation in both methods. When the exact double-counting treatment and a good projector to the correlated subspace are used, LDA+DMFT yields very accurate total energy and excitation spectrum of the H$_2$ molecule. We also discuss how this double-counting scheme can be extended to solid state calculations.