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Article Dans Une Revue Journal of Chemical Physics Année : 2011

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized ?: The 2v3 overtone of CO2

Michel Chrysos
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I.-A. Verzhbitskiy
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Florent Rachet
A.-P. Kouzov
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Résumé

Molecular vibrations that are not totally symmetrical give rise to depolarized lines [P. Atkins and J. de Paula, Atkins Physical Chemistry (Oxford University Press, UK, 2006), p. 464]. But in the case of stretching vibrations in centrosymmetric molecules, the statement has so far not been conclusively verified. It is the purpose of this article to report a rigorous experimental and theoretical analysis of the 2 nu(3) band of CO2-the first overtone of the asymmetrical stretch vibration. The anisotropic spectrum was extracted and its spectral moment calculated from light-scattering measurements, taken at room temperature and for a wide range of CO2-gas densities. Evidence for a near-entirely depolarized Raman band is provided, with integrated depolarization ratio eta(int) = 6/7.16, closely approaching the upper bound eta(max) = 6/7. Agreement with theoretical predictions is found, on the basis of quality ab initio data for polarizability properties, provided that electro-optical and mechanical anharmonicity and intermode coupling effects between symmetric nu(1) and antisymmetric nu(3) stretching vibrations are incorporated.

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Dates et versions

hal-03344660 , version 1 (15-09-2021)

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Michel Chrysos, I.-A. Verzhbitskiy, Florent Rachet, A.-P. Kouzov. Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized ?: The 2v3 overtone of CO2. Journal of Chemical Physics, 2011, 134 (4), Non spécifié. ⟨10.1063/1.3535599⟩. ⟨hal-03344660⟩
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