Pressure broadening of the electric dipole and Raman lines of CO2 by argon: stringent test of the classical impact theory at different temperatures on a benchmark system

Ivanov, S.V.; Buzykin, O.G.

Авторы: Ivanov S.V., Buzykin O.G.
Журнал: Journal of Quantitative Spectroscopy and Radiative Transfer
Том: 185
Год издания: 2016
Издательство: Pergamon Press Ltd.
Местоположение издательства: United Kingdom
Первая страница: 48
Последняя страница: 57
DOI: 10.1016/j.jqsrt.2016.08.017
Аннотация: A classical approach is applied to calculate pressure broadening coefficients of CO2 vibration-rotational spectral lines perturbed by Ar. Three types of spectra are examined: electric dipole (infrared) absorption; isotropic and anisotropic Raman Q branches. Simple and explicit formulae of the classical impact theory are used along with exact 3D Hamilton equations for CO2–Ar molecular motion. The calculations utilize vibrationally independent most accurate ab initio potential energy surface (PES) of Hutson et al. expanded in Legendre polynomial series up to lmax = 24. New improved algorithm of classical rotational frequency selection is applied. The dependences of CO2 half-widths on rotational quantum number J up to J=100 are computed for the temperatures between 77 and 765 K and compared with available experimental data as well as with the results of fully quantum dynamical calculations performed on the same PES. To make the picture complete, the predictions of two independent variants of the semi-classical Robert-Bonamy formalism for dipole absorption lines are included. This method. however, has demonstrated poor accuracy almost for all temperatures. On the contrary, classical broadening coefficients are in excellent agreement both with measurements and with quantum results at all temperatures. The classical impact theory in its present variant is capable to produce quickly and accurately the pressure broadening coefficients of spectral lines of linear molecules for any J value (including high Js) using full-dimensional ab initio - based PES in the cases where other computational methods are either extremely time consuming (like the quantum close coupling method) or give erroneous results (like semi-classical methods).
Добавил в систему: Иванов Сергей Викторович

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Pressure broadening of the electric dipole and Raman lines of CO2 by argon: stringent test of the classical impact theory at different temperatures on a benchmark systemстатья