Intermolecular Raman spectroscopy of long-range interactions:: The CO2-Ar collision-induced ν3 CO2 band

We report an exhaustive joint theoretical/experimental collision-induced Raman scattering (CIRS) study of the Raman-forbidden nu(3) band of CO2. Original zeroth and second anisotropic spectral moment formulas for CO2-Ar are derived, in which complete expressions of Raman amplitudes (derived by the authors with a recently reported universal method [Phys. Rev. A 74, 012723 (2006)]) are input. The method, applicable to any kind of spectroscopy and whatever the number of photons, molecules, or interaction involved, uses the irreducible spherical tensor formalism in conjunction with a Feynman-like diagrammatic technique to describe any long-range induced property mechanism. Experimentally, spectral moments are deduced from careful, absolute-scale, frequency-resolved CO2-Ar depolarized CIRS measurements of unprecedented accuracy. From comparison between theory and experiment, we provide quantitative evidence of a substantial contribution of a nonlinear dipole polarization mechanism, predicted theoretically in the preceding paper. In this mechanism, both photons are shown to interact with Ar (which then couples to CO2 via intermolecular interactions), rather than with both colliders that is the case in the standard dipole-induced quadrupole (DIQ) interaction. The effect had thus far escaped notice possibly because of the reduced accuracy of the earlier self-consistent field dipole-quadrupole polarizablity computations along with a lack of CIRS measurements. In light of recent extensive computations by Haskopoulos and Maroulis [Chem. Phys. Lett. 417, 235 (2006)], the improved ab initio data of these properties are found to corroborate our predictions, and confirm that the Raman amplitude owing to the dipole-dipole-quadrupole hyperpolarizability of the atomic perturber strongly and destructively interferes with the (otherwise dominant) DIQ Raman amplitude.