Interatomic Methods for the Dispersion Energy Derived from the Adiabatic Connection Fluctuation-Dissipation Theorem

TL;DR

This paper derives interatomic dispersion energy formulas from the ACFD theorem, clarifies their quantum mechanical basis, and introduces an efficient Hamiltonian diagonalization method for many-body dispersion calculations.

Contribution

It provides a rigorous derivation of pairwise dispersion energy from the ACFD theorem and demonstrates the equivalence of Hamiltonian diagonalization with ACFD in the RPA for quantum harmonic oscillators.

Findings

Dispersion energy emerges from the second-order expansion of ACFD.

Hamiltonian diagonalization is an efficient method for many-body dispersion.

Short-range damping arises from a screened Coulomb potential.

Abstract

Interatomic pairwise methods are currently among the most popular and accurate ways to include dispersion energy in density functional theory (DFT) calculations. However, when applied to more than two atoms, these methods are still frequently perceived to be based on \textit{ad hoc} assumptions, rather than a rigorous derivation from quantum mechanics. Starting from the adiabatic connection fluctuation-dissipation (ACFD) theorem, an exact expression for the electronic exchange-correlation energy, we demonstrate that the pairwise interatomic dispersion energy for an arbitrary collection of isotropic polarizable dipoles emerges from the second-order expansion of the ACFD formula. Moreover, for a system of quantum harmonic oscillators coupled through a dipole--dipole potential, we prove the equivalence between the full interaction energy obtained from the Hamiltonian diagonalization and the ACFD correlation energy in the random-phase approximation. This property makes the Hamiltonian diagonalization an efficient method for the calculation of the many-body dispersion energy. In addition, we show that the switching function used to damp the dispersion interaction at short distances arises from a short-range screened Coulomb potential, whose role is to account for the spatial spread of the individual atomic dipole moments. By using the ACFD formula we gain a deeper understanding of the approximations made in the interatomic pairwise approaches, providing a powerful formalism for further development of accurate and efficient methods for the calculation of the dispersion energy.