Semiclassical theory of molecular collisions: Real and complex-valued classical trajectories for collinear atom Morse oscillator collisions

Abstract

Real and complex-valued classical trajectories have been calculated for the collinear collision of an atom with a Morse oscillator. They are used in three semiclassical approximations for the transition probability: a Bessel uniform approximation, an Airy uniform approximation and a primitive semiclassical approximation. Comparison with exact quantum results shows that the Bessel uniform approximation is accurate even for near elastic collisions where the Airy and primitive approximations break down. The Airy and Bessel approximations agree quite closely for inelastic collisions however. The primitive semiclassical approximation is less accurate than either the Airy or Bessel approximation.