Journal of Chemical Physics, Vol.100, No.11, 7875-7889, 1994
Transient Changes in Polarizability for Centrosymmetric Linear-Molecules Interacting at Long-Range - Theory and Numerical Results for H-2...H-2, H-2...N-2, and N-2...N-2
Transient, collision-induced changes in polarizability Delta alpha on the subpicosecond time scale affect Rayleigh and rototranslational Raman scattering by diatomic molecules in dense gases and liquids, induced birefringence, impulsive stimulated scattering, and dielectric and refractivity virial coefficients. For pairs of D-infinity h molecules, this work gives the long-range contributions to bet complete through order R(-6) in the intermolecular separation R, including the first- and second-order dipole-induced-dipole (DID) interactions, higher-multipole induction, effects of the nonuniformity in the local field, hyperpolarization, and dispersion. We have used spherical tenser methods to cast Delta alpha into the symmetry-adapted form needed for spectroscopic line shape analysis. The polarization mechanisms included here give rise to isotropic rototranslational Raman scattering and to simultaneous rotational transitions on two interacting molecules; both are collision-induced phenomena. Transitions with Delta J up to +/-4 are produced by the R(-5) and R(-6) polarization mechanisms treated in this work (and the isotropic part of the pair potential). For the pairs H, H,, H-2...N-2, and N-2...N-2, we have used ab initio results for permanent multipoles and susceptibilities to evaluate the classical induction contributions to Delta alpha. For the dispersion contributions, we have derived exact results in the form of integrals of the polarizability and gamma hyperpolarizability over imaginary frequencies, and we have approximated these numerically in terms of the static alpha and gamma values, together with van der Waals energy coefficients. For the pairs and configurations studied, the first-order DID terms give the dominant contributions to Delta alpha; the agreement between these terms and the full long-range results tends to be better for the anisotropic collision-induced polarizability Delta alpha(2)(M) than for the isotropic part Delta alpha(O)(O), particularly for T-shaped pairs. The relative contributions to Delta alpha from the other polarization mechanisms reach as high as 29% for second-order DID terms, 27% for E-tensor terms (higher-multipole induction and local field nonuniformity), 21% for dispersion, and 8% for hyperpolarization effects, for R values similar to 0.5-1.0 a.u. outside the isotropic van der Waals minimum.
Keywords:DEPOLARIZED RAYLEIGH-SCATTERING;INDUCED LIGHT-SCATTERING;LIQUID CARBON-DISULFIDE;REFRACTIVITY VIRIAL-COEFFICIENTS;INTERPARTICLE PAIR CORRELATIONS;INTERACTION-INDUCED SPECTRA;INDUCED FLUCTUATION CORRELATIONS;INDUCED RAMAN-SCATTERING;VANDERWAALS INTERACTIONS;COMPUTER-SIMULATION