Collisional broadening and spectral line shape of an entire rotational band

Abstract

The impact approximation is applied to the classical binary collision operator making it possible to derive an expression for the dipole correlation function for real systems in a form which is computationally tractable and contains no adjustable parameters. Trajectory calculations are performed (in order to evaluate the microscopic expression for the relaxation parameter in the correlation function) for the system CO in dense Ar gas. Comparison is made with experimental data and excellent agreement is found for certain densities when a quantum correction is included. At higher densities (i.e., ρ^(−1/3)< "the range of the potential") one approximation is not valid and comparison with experiment illustrates this point.

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