Diffusion approximations of the two-dimensional master equation

摘要

The effects of rotational energy transfer on unimolecular dissociation are assessed using a two-dimensional master equation approach. The collision operator for such a system can be very large, and approximations are sought that reduce the size of the matrix that has to be stored. The density of states of the vibrational energy is large for most molecules and can be treated as virtually continuous. As a consequence, motion in vibrational energy space can be treated using a diffusion equation approach. This reduces the storage requirements greatly and increases the speed at which diagonalization occurs. Results are presented for the dissociation of ethane and methane.