Fully quantum calculations of the line shape parameters for 1-0 P(22) and P(31) lines of CO perturbed by He or Ar

• Published in: The Journal of chemical physics Vol. 157; no. 22; p. 224301
• Main Authors: Chai, Shijie, Chen, Qixin, Yang, Dongzheng, Zhou, Yanzi, Xie, Daiqian
• Format: Journal Article
• Language: English
• Published: United States 14.12.2022
• ISSN: 1089-7690
• DOI: 10.1063/5.0124989

This work reports the full quantum calculations of the spectral line shape parameters for the P(22) line of CO and the P(31) line of CO in the fundamental band perturbed by He or Ar from 20 to 1000 K for the first time. The generalized spectroscopic cross sections of CO-He/Ar indicate that the Dicke narrowing effect competes with the pressure broadening effect. The pressure broadening can be explained by the dynamic behaviors of intermolecular collisions. The intermolecular inelastic collisions contribute more than 95% to the pressure broadening in both CO-He and CO-Ar systems at high temperatures. Regarding the state-to-state inelastic contributions to pressure broadening, the maximum contribution out of the final state of a given line is close to that out of the initial state. The Dicke narrowing effect influences the line shape profile significantly at high temperatures, which suggests that it is indispensable for reproducing the spectral line profile. With the Dicke narrowing effect, the calculated pressure-broadening coefficients and spectral intensity distribution are in good agreement with the available experimental observations.