Efficient and accurate surface hopping for long time nonadiabatic quantum dynamics
- Department of Chemistry, Stanford University, Stanford, California 94305 (United States)
The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic 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 paper we show that 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 nonadiabatic regimes, making it computationally tractable to treat the quantum dynamics of complex systems for long times. We demonstrate our approach by applying it to a model of condensed phase charge transfer where 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.
- OSTI ID:
- 22121602
- Journal Information:
- Journal of Chemical Physics, Vol. 139, Issue 1; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Efficient on-the-fly ab initio semiclassical method for computing time-resolved nonadiabatic electronic spectra with surface hopping or Ehrenfest dynamics
Accurate nonadiabatic quantum dynamics on the cheap: Making the most of mean field theory with master equations