The Ehrenfest method with quantum corrections to simulate the relaxation of molecules in solution: Equilibrium and dynamics

摘要

The use of the Ehrenfest method to simulate the relaxation of molecules in solution is explored. Using the cyanide ion dissolved in water as a test model, the independent trajectory (IT) and the bundle of trajectories (BT) approximations are shown to provide very different results for the time evolution of the vibrational populations of the solute. None of these approximations reproduce the Boltzmann equilibrium vibrational populations accurately. A modification of the Ehrenfest method based on the use of quantum correction factors is thus proposed to solve this problem. The simulations carried out using the modified Ehrenfest method provide IT and BT relaxation times which are closer to each other and which agree quite well with previous hybrid perturbative results. (c) 2007 American Institute of Physics.