Fewest switches adiabatic surface hopping as applied to vibrational energy relaxation.
In this contribution quantum/classical surface hopping methodology is applied to vibrational energy relaxation of a quantum oscillator in a classical heat bath. The model of a linearly damped (harmonic) oscillator is chosen which can be mapped onto the Brownian motion (Caldeira-Leggett) Hamiltonian. In the simulations Tully's fewest switches surface hopping scheme is adopted with inclusion of dephasing in the adiabatic basis using a simple decoherence algorithm. The results are compared to the predictions of a Redfield-type quantum master equation modeling using the classical heat bath force correlation function as input. Thereby a link is established between both types of quantum/classical approaches. Viewed from the latter perspective, surface hopping with dephasing may be interpreted as "on-the-fly" stochastic realization of a quantum/classical Pauli master equation.
Käb
Günter
G
Max-Planck-Institut für Biophysikalische Chemie, Am Fassberg 11, D-37077 Göttingen, Germany. gkaeb@gwdg.de
D006207:Half-Life; D011789:Quantum Theory; D013269:Stochastic Processes; D013696:Temperature; D014732:Vibration