Density Functional Calculations Based on the Exponential Ansatz.

Abstract

This work explores the application of the singles-based exponential ansatz to density functional calculations. In contrast to the standard approach where Kohn-Sham (KS) orbitals are determined prior to computing molecular quantities of interest, we consider the single-reference Hartree-Fock wave function as a starting point. Applying the exponential ansatz to this single reference gives an auxiliary wave function that is employed to calculate the electronic properties of the system. This wave function is determined self-consistently through the standard KS Hamiltonian but evaluated over the Hartree-Fock molecular orbital basis. By using spin-symmetry breaking, we recover size-consistent results free of unphysical fractional charges in the dissociation limit. Our method shows consistency with standard KS density functional calculations when the system geometry is similar to the equilibrium one or in repulsive configurations. For moderately long distances between atoms, not at dissociation, because of self-interaction the exponential ansatz may give instabilities in the form of large cluster amplitudes. To avoid these, this work introduces a relatively simple regularization method that preserves size-consistency and penalizes high amplitudes of the cluster operator, whereas the results remain physically meaningful. We also present the time-dependent extension of our theory and show that it can feature quantum states where multiple electrons are excited.