The air-broadened, near-infrared CO2 line shape in the spectrally isolated regime: evidence of simultaneous Dicke narrowing and speed dependence

• Published in: The Journal of chemical physics Vol. 135; no. 6; p. 064308
• Main Authors: Long, David A, Bielska, Katarzyna, Lisak, Daniel, Havey, Daniel K, Okumura, Mitchio, Miller, Charles E, Hodges, Joseph T
• Format: Journal Article
• Language: English
• Published: United States 14.08.2011
• Subjects: Air; Carbon Dioxide - chemistry; Databases, Factual; Models, Theoretical; Pressure; Spectroscopy, Near-Infrared - statistics & numerical data
• ISSN: 1089-7690
• DOI: 10.1063/1.3624527

Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was employed to measure air-broadened CO(2) line shape parameters for transitions near 1.6 μm over a pressure range of 6.7-33 kPa. The high sensitivity of FS-CRDS allowed for the first measurements in this wavelength range of air-broadened line shape parameters on samples with CO(2) mixing ratios near those of the atmosphere. The measured air-broadening parameters show several percent deviations (0.9%-2.7%) from values found in the HITRAN 2008 database. Spectra were fit with a variety of models including the Voigt, Galatry, Nelkin-Ghatak, and speed-dependent Nelkin-Ghatak line profiles. Clear evidence of line narrowing was observed, which if unaccounted for can lead to several percent biases. Furthermore, it was observed that only the speed-dependent Nelkin-Ghatak line profile was able to model the spectra to within the instrumental noise level because of the concurrent effects of collisional narrowing and speed dependence of collisional broadening and shifting.