Speed dependence of collisional relaxation in ground vibrational state of OCS: Rotational behaviour

Accurate experimental data on pressure broadened profiles of (OCS)-O-16-C-12-S-32 pure rotational lines in a broad range of quantum number J have been analyzed taking into account the speed dependence of collisional relaxation. Refined values of collisional self-broadening coefficients are determined and compared to previously known data. New quantitative information on departures of observed line shapes from the traditional Voigt profile is obtained. It is shown that these departures result mainly from the speed dependence of collisional relaxation. Theoretical calculations of self-broadening parameters are performed in the framework of the semiclassical impact Robert-Bonamy formalism where the mean relative molecular speed as well as the Maxwell-Boltzmann distribution of relative speeds is considered. The necessity of allowance for the speed dependence in line shape models is confirmed and satisfactory results have been obtained by arbitrarily limiting the integration of the differential cross section to a finite value of the impact parameter. It is shown for the first time for the whole rotational spectrum that speed dependent models not only improve accuracy of modeling the observed line profiles but also give physically grounded values of collisional relaxation parameters. (C) 2012 American Institute of Physics. [http://dx.doi.org/ 10.1063/1.3696895]