Quantum statistical theory of laser-stimulated surface processes. Part 2: Nonequilibrium rate of laser excitation and multiphonon relaxation

By means of quantum statistical theory, the laser excitation rate and multiphonon relaxation rate are calculated for species adsorbed on cold and heated surfaces. The complex frequency of Bose operators is derived from a microscopic Hamiltonian with anharmonic mode-mode coupling, which provides the origin of the non-Arrhenius form for the multi-phonon relaxation rate. The energy transfer rate due to the interference effects between the coherent laser excitation and multiphonon coupling is calculated. The nonequilibrium energy transfer rate due to the energy feedback of the heated surface is investigated via a self-consistent heat diffusion equation.