Dispersion dipoles for coupled Drude oscillators

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Abstract

We present the dispersion-induced dipole moments of coupled Drude oscillators obtained from two approaches. The first approach evaluates the dipole moment using the second-order Rayleigh-Schrödinger perturbation theory wave function allowing for dipole-dipole and dipole-quadrupole coupling. The second approach, based on response theory, employs an integral of the dipole-dipole polarizability of one oscillator and the dipole-dipole-quadrupole hyperpolarizability of the other oscillator over imaginary frequencies. The resulting dispersion dipoles exhibit an R-7 dependence on the separation between the two oscillators and are connected to the leading-order C6/R6 dispersion energy through the electrostatic Hellmann-Feynman theorem.

Original languageEnglish
Article number034111
JournalJournal of Chemical Physics
Volume144
Issue number3
DOIs
StatePublished - Jan 21 2016
Externally publishedYes

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