Correlation between normal character and Raman intensities of isotopologues of carbon dioxide

Abstract:Previous studies on the vibrational structure of carbon dioxide isotopologues have revealed a correlation between the strength of Fermi interactions and a recently defined normal-mode parameter. In this contribution, we investigate how the Raman intensities of the most intense bands evolve across the complete series of carbon dioxide isotopologues at room temperature. To this end, we introduce a general scheme for simulating Raman intensities in linear triatomic molecules, based on the computation of the mean polarizability surface up to cubic terms for all twelve stable species. For the first time, we establish correlations between the degree of normality and the Raman transition intensities, mean polarizability derivatives, and variational Raman shift errors across the CO$_2$ isotopologue series. The observed trends are further analyzed by considering rotational contributions, which may partially account for the deviations observed in the correlations. Our study is supported by experimental Raman spectra of isotopically enriched samples and theoretical simulations. Although this study focuses on carbon dioxide, similar behavior is expected for other series of isotopologues.

Chemical Physics (physics.chem-ph); Quantum Physics (quant-ph)

arXiv:2610.21707 [physics.chem-ph]

(or arXiv:2610.21707v1 [physics.chem-ph] for this version)

https://doi.org/10.48550/arXiv.2610.21707 Focus to learn more arXiv-issued DOI via DataCite (pending registration)

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