Consistent treatment of coherent and incoherent energy transfer dynamics using a variational master equation.

J Chem Phys

Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom.

Published: September 2011

We investigate the energy transfer dynamics in a donor-acceptor model by developing a time-local master equation technique based on a variational transformation of the underlying Hamiltonian. The variational transformation allows a minimisation of the Hamiltonian perturbation term dependent on the system parameters, and consequently results in a versatile master equation valid over a range of system-bath coupling strengths, temperatures, and environmental spectral densities. While our formalism reduces to the well-known Redfield, Förster and polaron forms in the appropriate limits, in general it is not equivalent to perturbing in either the system-environment or donor-acceptor coupling strengths, and hence can provide reliable results between these limits as well. Moreover, we show how to include the effects of both environmental correlations and non-equilibrium preparations within the formalism.

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http://dx.doi.org/10.1063/1.3636081DOI Listing

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