Journal of Physical Chemistry A, Vol.117, No.46, 11837-11846, 2013
Argon-Induced Pressure Broadening, Shifting, and Narrowing in the CN A(2)Pi X-2 Sigma(+) (1-0) Band
Selected isolated rotational transitions in the 1-0 band of the red A(2)Pi-X E-2(+) 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.