HALFWIDTHS AND LINE SHIFTS OF $H_{2}O$ TRANSITIONS BROADENED BY $CO_{2}$

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1996

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Ohio State University

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The complex semiclassical formalism of Robert and Bonamy $^{a,b}$ is used to calculate both halfwidths and line shifts for water vapor in a bath of carbon dioxide gas. The assumed intermolecular potential is a combination of electrostatic, Lennard-Jones 6-12 atom-atom (expanded to 8th order), induction, and dispersion terms. Calculations are made for transitions in the $\nu_{1}$, $2\nu_{2}$, and $\nu_{3}$ vibrational band and are compared with the measurements of Gamache et al. $c$ Good agreement with the experimental results is observed for both the halfwidth and line shifts. It is shown that the imaginary parts are important for both the line shift and halfwidth calculations.

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$^{a}$D. Robert and J. Bonamy, ""Short range force effects in semiclassical molecular line broadening calculations"", J. Phys. (Paris) 40, 923 (1979) $^{b}$R. Lynch, R. R. Gamache, and S. P. Neshyba, ""Fully Complex Implementation of the Robert- Bonamy Formalism: Halfwidths and Line Shifts of $H_{2}O$ Broadened by $N_{2}$,"" submitted to J. Chem. Phys. November, 1995. $^{c}$R. R. Gamache, S. P. Neshyba, J. J. Plateaux, A. Barbe, L Rgalia, and J. B. Pollack, J. Mol. Spectrosc. 170, 131 (1995).
Author Institution: Department of Environmental, Earth, and Atmospheric Sciences and Center for Atmospheric Research, University of Massachusetts; Wentworth Institute of Technology, University of Massachusetts

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