Van der Waals interactions: Evaluations by use of a statistical mechanical method

TL;DR

This paper demonstrates that the Casimir-Polder and van der Waals interactions are equivalent at short distances using a statistical mechanical approach, suggesting improvements in molecular energy calculations.

Contribution

It introduces a statistical mechanical method to evaluate van der Waals and Casimir-Polder interactions, establishing their equivalence at short separations.

Findings

The statistical mechanical method confirms the equivalence of interactions at short distances.

The approach allows for numerical estimates of Casimir energy in molecular systems.

Adding Casimir energy corrections can enhance molecular energy calculations.

Abstract

In this work the induced van der Waals interaction between a pair of neutral atoms or molecules is considered by use of a statistical mechanical method. Commonly this interaction is obtained by standard quantum mechanical perturbation theory to second order. However, the latter is restricted to electrostatic interactions between charges and dipole moments. So with radiating dipole-dipole interaction where retardation effects are important for large separations of the particles, other methods are needed, and the resulting induced interaction is the Casimir-Polder interaction usually obtained by field theory. It can also be evaluated, however, by a statistical mechanical method that utilizes the path integral representation. We here show explicitly by use of the statistical mechanical method the equivalence of the Casimir-Polder and van der Waals interactions to leading order for short separations where retardation effects can be neglected. Physically this is well known, but in our opinion the mathematics of this transition process is not so obvious. The evaluations needed mean a transform of the statistical mechanical free energy expression to a form that can be identified with second order perturbation theory. In recent works [H{\o}ye 2010] the Casimir-Polder or Casimir energy has been added as a correction to calculations of systems like the electron clouds of molecules. The equivalence to van der Waals interactions to leading order indicates that the added Casimir energy will improve the accuracy of calculated molecular energies. We here also give numerical estimates of this energy including analysis and estimates for the uniform electron gas.