The quantum-classical Liouville equation offers a rigorous approach to non-adiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing to unfavorable numerical scaling. In this talk I will discuss how this problem can be alleviated by combining it with a formally exact generalized quantum master equation treatment. This allows dramatic improvements in the efficiency of the approach in non-adiabatic regimes, making it computationally tractable to treat the quantum dynamics of complex systems for long times. I will demonstrate the utility our approach by showing its performance in treating the non-equilibrium relaxation in models of condensed phase charge transfer. In these problems our method is shown to be numerically exact in regimes where fewest-switches surface hopping and mean field approaches fail to obtain either the correct rates or long-time populations.

Efficient and accurate surface hopping for long time non-adiabatic quantum dynamics

246th National Meeting (2013)

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