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Analytical Evaluation of the Maxwell–Boltzmann Velocity Average in Pressure-Broadened Half-Width Calculations

✍ Scribed by Robert R. Gamache


Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
170 KB
Volume
208
Category
Article
ISSN
0022-2852

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✦ Synopsis


For the first time the half-width within the complex Robert-Bonamy (CRB) formalism is calculated without making the mean relative thermal velocity approximation. The application is to the nitrogen-broadened half-width of the 500.4-GHz transition (34 2 32 ← 34 1 33 ) of the ground vibrational state of ozone. For each state of the perturber, the optical cross sections are determined at a number of velocities with the intermolecular potential taken as a sum of electrostatic contributions and Lennard-Jones (6-12) atom-atom components. The dynamics of the collision process are correct to second order in time. Using a nonlinear least-squares fitting method, the optical cross sections are fit to a double power law, which allows the velocity integral for the half-width to be done analytically. The results are compared with the mean relative thermal velocity complex Robert-Bonamy calculations and with measurement. The temperature dependence of the half-width, which is necessary for reduction of remotely sensed data, is determined from both methods and compared with experiment.