New expressions for the van der Waals contribution to the collision-induced, static polarizability of a molecular pair (ΔαvdW) are derived within a reaction-field theory. For molecules interacting at long range, multipole expansions are used to determine the reaction field; at shorter range, where overlap is small but nonnegligible, the derivation is based on a nonlocal polarizability density model. In both cases, we obtain ΔαvdW in terms of integrals over imaginary frequencies, each involving the product of a hyperpolarizability for one molecule and a polarizability or hyperpolarizability for the other molecule. In addition, we show that the polarizability changes induced by van der Waals interactions between two molecules stem from two distinct physical effects. First, in an applied field F, each molecule is polarized nonlinearly by the simultaneous action of the field due to the fluctuating charge distribution of its neighbor and the field F. Second, the applied field F alters the correlations between the spontaneous, quantum mechanical fluctuations in the charge density of each molecule, thus affecting its interaction with the neighboring molecule. Effects of field-induced fluctuation correlations have not been included in earlier models for the van der Waals contributions to pair polarizabilities.
Read full abstract