Mixed quantum-classical evolution in open molecular systems

RESUMO

We consider a mixed quantum-classical formulation for open nonequilibrium molecular systems. We employ the pseudoparticle nonequilibrium Green's function (PP-NEGF) method as a fully quantum description and a starting point for introducing classical nuclear dynamics for an open system. We use this formulation to derive a density-matrix equation of motion describing the quantum-classical evolution. We compare our results with previous formulations and highlight important differences related to the nonequilibrium and open character of the molecular system. We also analyze the approximations needed to reduce full quantum-classical dynamics to the fewest-switches surface hopping (FSSH) method and show that these approximations are unreasonable when adiabatic surfaces come close to each other.