Generalized quantum kinetic expansion: Higher-order corrections to multichromophoric Förster theory

J Chem Phys. 2015 Aug 21;143(7):074102. doi: 10.1063/1.4928634.

Abstract

For a general two-cluster energy transfer network, a new methodology of the generalized quantum kinetic expansion (GQKE) method is developed, which predicts an exact time-convolution equation for the cluster population evolution under the initial condition of the local cluster equilibrium state. The cluster-to-cluster rate kernel is expanded over the inter-cluster couplings. The lowest second-order GQKE rate recovers the multichromophoric Förster theory (MCFT) rate. The higher-order corrections to the MCFT rate are systematically included using the continued fraction resummation form, resulting in the resummed GQKE method. The reliability of the GQKE methodology is verified in two model systems, revealing the relevance of higher-order corrections.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bacterial Proteins / chemistry
  • Bacteriochlorophylls / chemistry
  • Fluorescence Resonance Energy Transfer*
  • Kinetics
  • Light-Harvesting Protein Complexes / chemistry
  • Models, Chemical*
  • Quantum Theory*

Substances

  • Bacterial Proteins
  • Bacteriochlorophylls
  • FMO bacteriochlorophyll protein, Bacteria
  • Light-Harvesting Protein Complexes