The collision-induced polarizability of a pair of hydrogen molecules

摘要

Collision-induced light scattering, impulsive stimulated scattering, and subpicosecond-induced birefringence all depend on the transient changes Delta alpha in molecular polarizabilities that occur when molecules collide. Ab initio results for Delta alpha are needed to permit comparisons with accurate experimental results for these spectra and for refractive index virial coefficients and dielectric virial coefficients. In this work, we provide results for Delta alpha for a pair of hydrogen molecules, treated at CCSD(T) level, with an aug-cc-pV5Z (spdf) basis set. Our values replace the best previous ab initio results for the variation of Delta alpha with intermolecular separation, the self-consistent-field results obtained by Bounds [Mol. Phys. 38, 2099 (1979)] with a relatively small (3s2p) basis set for H-2. For the six geometrical configurations studied by Bounds, the inclusion of correlation and improvements in the basis tend to increase both the trace Delta alpha(0)(0) and the anisotropy Delta alpha(m)(2) of the pair polarizability. The change in the anisotropy is relatively small, but our values for the trace differ by factors of 2 or more from Bounds' results. For use in computing experimental line shapes, intensities, and virial coefficients, we have calculated Delta alpha for 18 different relative orientations of a pair of H-2 molecules, with the intermolecular separation R ranging from 2 a.u. (3 a.u. for a linear pair) to 10 a.u. The H-2 bond length is fixed at the vibrationally averaged internuclear separation in the ground state r=1.449 a.u. Our results agree well with the CCSD(T) results for Delta alpha obtained by Maroulis [J. Phys. Chem. A 104, 4772 (2000)] for two pair configurations of H-2 center dot H-2 (linear and T-shaped) at a fixed internuclear distance of R=6.5 a.u. in a [6s4p1d] basis. As the intermolecular distance increases (for R >= 8 a.u.), the spherical-tensor components of Delta alpha converge to the results from a long-range model that includes dipole-induced-dipole (DID) interactions, higher-multipole induction, nonuniformity of the local field, hyperpolarization, and van der Waals dispersion. Deviations from the first-order DID model are still evident for R between 8 and 10 a.u. in most orientations of the pair. At shorter range, overlap damping, exchange, and orbital distortion reduce both Delta alpha(0)(0) and Delta alpha(0)(2) below their long-range limiting forms. (c) 2007 American Institute of Physics.