A study of finite-size and non-perturbative effects on the van der Waals and the Casimir-Polder forces

University dissertation from Stockholm : KTH Royal Institute of Technology

Abstract: This licentiate thesis addresses two important aspects of the van der Waals and the Casimir-Polder ground-state and excited-state (resonance) interactions between two atoms or molecules. The first is the finite-size effect and the second is the non-perturbative effect. Going beyond the usual assumption of atoms and molecules as point particles and adopting a description of finite size, the divergence inherent in such interaction energies in the limit of zero separation distance between the two interacting atoms or molecules is removed. The attainment of finite interaction energy at such close separation distance facilitates the estimation of van der Waals force contribution to the binding energy of the molecules, and towards surfaces. This is particularly important for noble atoms. We investigate in detail for a pair of helium (He) atoms and krypton (Kr) atoms, and for a pair of methane (CH4) molecules considering its environmental importance. The application of finite size further leads to finite self energies of the atoms. The expression of the interaction energy, as is discussed in detail in this thesis, typically contains a logarithmic factor of the form ln(1-x). Formerly, in evaluating the interaction energies, this factor is customarily series-expanded and truncated in the leading order with certain assumptions. This thesis explores the effect of using the full expression, which we refer to as the non-perturbative (or, the non-expanded) theory, analytically wherever possible as well as numerically. The combined application of the finite-size theory and the non-perturbative theory results in as much as 100% correction in the self energy of atoms in vacuum. This may give rise to significant physical consequences, for example, in the permeabilities of atoms across dielectric membranes. The non-perturbative theory, in addition, exhibits interesting behaviour in the retarded resonance interaction.