Argon-Induced Pressure Broadening, Shifting, and Narrowing in the CN A2Π X2Σ+ (1-0) Band

被引:9
作者
Forthomme, Damien [1 ]
McRaven, Christopher P. [1 ]
Sears, Trevor J. [1 ,2 ]
Hall, Gregory E. [1 ]
机构
[1] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
[2] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
关键词
ROTATIONAL ENERGY-TRANSFER; SPECTRAL-LINE SHAPES; STATE-TO-STATE; FREQUENCY-MODULATION; SPEED DEPENDENCE; MOLECULAR-COLLISIONS; FUNDAMENTAL-BAND; RATE CONSTANTS; IMPACT THEORY; AR;
D O I
10.1021/jp4030359
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
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页码:11837 / 11846
页数:10
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