Calculation of coherences in Foerster and modified Redfield theories of excitation energy transfer

Abstract

Foerster and modified Redfield theories play one of the central roles in the description of excitation energy transfer in molecular systems. However, in the present state, these theories describe only the dynamics of populations of local electronic excitations or delocalized exciton eigenstates, respectively, i.e., the diagonal elements of the density matrix in the corresponding representation. They do not give prescription for propagating the off-diagonal elements of the density matrix (coherences). This is commonly accepted as a limitation of these theories. Here we derive formulas for the dynamics of the coherences in the framework of Foerster and modified Redfield theories and, thus, remove this limitation. These formulas provide excellent correspondence with numerically exact calculations according to the hierarchical equations of motion. Also we show that, even within the range of applicability of the standard Redfield theory, the formulas for coherences derived in the framework of the modified Redfield theory provide, in some cases, more precise results.

15 pages, 9 figures

References in corpus (3)

• Delocalized excitons in natural light harvesting complexes
• The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae
• Ultrafast Energy Transfer with Competing Channels: Non-equilibrium Foerster and Modified Redfield Theories

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