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Molecular dynamics simulations for CO2 spectra. III. Permanent and collision-induced tensors contributions to light absorption and scattering

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Hartmann, J.-.-M., & Boulet, C. (2011). Molecular dynamics simulations for CO2 spectra. III. Permanent and collision-induced tensors contributions to light absorption and scattering. JOURNAL OF CHEMICAL PHYSICS, 134(18): 184312. doi:10.1063/1.3589143.

Classical molecular dynamics simulations have been performed for gaseous CO2 starting from an accurate anisotropic intermolecular potential. Through calculations of the evolutions of the positions and orientations of a large number of molecules, the time evolutions of the permanent and collision-induced electric dipole vector and polarizability tensor are obtained. These are computed from knowledge of static molecular parameters taking only the leading induction terms into account. The Laplace transforms of the auto-correlation functions of these tensors then directly yield the light absorption and scattering spectra. These predictions are, to our knowledge, the first in which the contributions of permanent and collision-induced tensors are simultaneously taken into account for gaseous CO2, without any adjusted parameter. Comparisons between computations and measurements are made for absorption in the region of the nu(3) infrared band and for depolarized Rayleigh scattering in the roto-translational band. They demonstrate the quality of the model over spectral ranges from the band center to the far wings where the spectrum varies by several orders of magnitude. The contributions of the permanent and interaction-induced (dipole and polarizability) tensors are analyzed for the first time, through the purely permanent (allowed), purely induced, and cross permanent/induced components of the spectra. It is shown that, while the purely induced contribution is negligible when compared to the collision-broadened allowed component, the cross term due to interferences between permanent and induced tensors significantly participates to the wings of the bands. This successfully clarifies the long lasting, confusing situation for the mechanisms governing the wings of the CO2 spectra considered in this work (c) 2011 American Institute of Physics. [doi: 10.1063/1.3589143]