Comparison of classical, distorted wave, and straight path methods of evaluating the integrals over the intermolecular trajectory during molecular collisions

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Abstract
The integrals over the intermolecular trajectory, relevant to pressure‐broadening and energy transfer calculations, are evaluated for the classical path, straight path, and distorted wave approximations. The present work, coupled with previous published work, leads to the conclusion that the three approximations agree to within 25% for near‐resonant collisions involving reduced energies E*≳1. For nonresonant collisions the classical calculation, which does not conserve energy, is in surprisingly good agreement with the distorted wave results even when the energy mismatch is one‐half of the incident energy.