Authors
Alexandre Tkatchenko, Alberto Ambrosetti, Robert A DiStasio
Publication date
2013/2/21
Journal
The Journal of Chemical Physics
Volume
138
Issue
7
Publisher
AIP Publishing
Description
Interatomic pairwise methods are currently among the most popular and accurate ways to include dispersion energy in density functional theory calculations. However, when applied to more than two atoms, these methods are still frequently perceived to be based on 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 upon invoking the random-phase approximation (RPA) or the full-potential approximation. Moreover, for a system of quantum harmonic oscillators coupled through a dipole-dipole potential, we prove the equivalence between the full interaction …
Total citations
201320142015201620172018201920202021202220232024111918221416231315141611