Variational mixed quantum/semiclassical simulation of dihalogen guest and rare-gas solid host dynamics.

摘要: A variational mixed quantum-semiclassical theory for the internal nuclear dynamics of a small molecule and induced small-amplitude coherent motion low-temperature host medium is developed, tested, used to simulate temporal evolution nonstationary states molecular surrounding degrees freedom. In this theory, termed Fixed Vibrational Basis/Gaussian Bath (FVB/GB) method, system treated fully quantum mechanically while Gaussian wave packets are bath An approximate time-dependent function entire model obtained instead just reduced density matrix, so enables analysis entangled that ensues following initial displacement internal-molecular (system) coordinate from its equilibrium position. The norm- energy-conserving properties propagation our trial natural consequences Dirac-Frenkel-McLachlan principle. approach also stabilizes time in comparison same ansatz propagated under previously employed locally quadratic approximation potential system-bath interaction terms bath-parameter equations motion. Dynamics calculations carried out iodine 2D krypton lattice reveal both time-course vibrational decoherence details host-atom accompanying energy dissipation dephasing. This work sets stage comprehensive simulation ultrafast time-resolved optical experiments on molecules solids.