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Article Dans Une Revue Chemical Physics Année : 2010

The importance of initial correlations in rate dynamics: A consistent non-Markovian master equation approach

A. Pomyalov
  • Fonction : Auteur
David J. Tannor
  • Fonction : Auteur

Résumé

The non-Markovian master equation is applied to the calculation of reaction rates. Starting from the flux-side correlation function form, we treat both the thermal and real time evolution consistently within second order perturbation theory in the system-bath coupling. It is shown that the non-Markovian dynamics enter formally not only in the time propagation but also in the expressions for the initial system-bath correlations. We show that these initial correlations can have a significant effect on the reaction rate. The method presented, although approximate, is an effective way to calculate reaction rates for weakly coupled systems over a wide range of temperatures. As such it provides a complementary approach to the exact treatment based on the ML-MCTDH method of Craig et al. [1], which serves as reference in this work.

Dates et versions

hal-00935155 , version 1 (23-01-2014)

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Citer

A. Pomyalov, Christoph Meier, David J. Tannor. The importance of initial correlations in rate dynamics: A consistent non-Markovian master equation approach. Chemical Physics, 2010, 370 (1-3), pp.98-108. ⟨10.1016/j.chemphys.2010.02.017⟩. ⟨hal-00935155⟩
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