Mixed quantum-classical theory for the collisional energy transfer and the rovibrational energy flow: Application to ozone stabilization

A mixed quantum-classical approach to the description of collisional energy transfer is proposed in which the vibrational motion of an energized molecule is treated quantum mechanically using wave packets, while the collisional motion of the molecule and quencher and the rotational motion of the molecule are treated using classical trajectories. This accounts rigorously for quantization of vibrational states, zero-point energy, scattering resonances, and permutation symmetry of identical atoms, while advantage is taken of the classical scattering regime. Energy is exchanged between vibrational, rotational, and translational degrees of freedom while the total energy is conserved. Application of this method to stabilization of the van der Waals states in ozone is presented. Examples of mixed quantum-classical trajectories are discussed, including an interesting example of supercollision. When combined with an efficient grid mapping procedure and the reduced dimensionality approximation, the method becomes very affordable computationally. (C) 2011 American Institute of Physics. [doi:10.1063/1.3576103]