Decoherent histories and nonadiabatic quantum molecular dynamics simulations

The role of quantum coherence loss in mixed quantum-classical dynamical systems is explored in the context of the theory of quantum decoherence introduced recently by Bittner and Rossky [J. Chem. Phys. 103, 8130 (1995)]. This theory, which is based upon the consistent histories interpretation of quantum mechanics, introduces decoherence in the quantum subsystem by carefully considering the relevant time and length scales over which one must consider the effects of phase interference between alternative histories of the classical subsystem. Such alternative histories are an integral part of any quantum-classical computational scheme which employs transitions between discrete quantum states; consequently, the coherences between alternative histories have a profound effect on the transition probability between quantum states. In this paper, we review the Bittner-Rossky theory and detail a computational algorithm suitable for large-scale quantum molecular dynamics simulations which implements this theory. Application of the algorithm towards the relaxation of a photoexcited aqueous electron compare well to previous estimates of the excited state survival time as well as to the experimental measurements. (C) 1997 American Institute of Physics. [S0021-9606(97)50944-5].