On the additivity of atomic and molecular dipole properties and dispersion energies using H, N, O, H2, N2, O2, NO, N2O, NH3and H2O as models

Abstract

The zeroth-order theory of intermolecular forces is used to derive additivity relations for rotationally averaged molecular dipole properties and dispersion energy constants by assuming that a molecule is comprised of non-interacting atoms or molecules. Some of the additivity rules are new and others, for example the mixture rule for dipole oscillator strength distributions (DOSDs), Bragg's rule for stopping cross sections and Landolt's rule for molecular refractivities, are well known. The additivity rules are tested by using previously constructed DOSDs and reliable values for the dipole oscillator strength sums Sk , Lk and Ik , and dispersion energy constants C 6, for H, N, O, H2, N2, O2, NO, N2O, NH3 and H2O as models. It is found that additivity is generally unreliable for estimating molecular properties corresponding to k < -2. Generally for k ≥ -2 and for C 6, and if the hydrogen molecule is used to represent the hydrogen atom in the additivity rules, the additivity relations yield results that are...