Selected isolated rotational transitions in the 1-0 band of the red A(2)Π-X (2)Σ(+) system in CN have been recorded with transient frequency modulation spectroscopy as a function of argon pressure up to 0.2 atm at room temperature. Line shapes were fit using Fourier transforms of a parametrized time correlation function, including Doppler and velocity-dependent collisional broadening, and collisional shifts. Deviations from Voigt line shapes can be equally well fit by modeling the narrowing with a speed-dependent collision model or with a velocity-changing collisional narrowing model. Pressure broadening coefficients were observed with little rotational state dependence, in the range of 0.070-0.075 cm(-1) atm(-1). In contrast, stronger and qualitatively different rotational state dependences are observed for both pressure-dependent blue shift coefficients and the narrowing parameters. No asymmetry in the pressure broadened lines was observed.
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http://dx.doi.org/10.1021/jp4030359 | DOI Listing |
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