Optimization of exciton trapping in energy transfer processes

J Phys Chem A. 2009 Dec 17;113(50):13825-38. doi: 10.1021/jp9032589.

Abstract

In this paper, we establish optimal conditions for maximal energy transfer efficiency using solutions for multilevel systems and interpret these analytical solutions with more intuitive kinetic networks resulting from a systematic mapping procedure. The mapping procedure defines an effective hopping rate as the leading order picture and nonlocal kinetic couplings as the quantum correction, hence leading to a rigorous separation of thermal hopping and coherent transfer useful for visualizing pathway connectivity and interference in quantum networks. As a result of these calculations, the dissipative effects of the surrounding environments can be optimized to yield the maximal efficiency, and modulation of the efficiency can be achieved using the cumulative quantum phase along any closed loops. The optimal coupling of the system and its environments is interpreted with the generic mechanisms: (i) balancing localized trapping and delocalized coherence, (ii) reducing the effective detuning via homogeneous line-broadening, (iii) suppressing the destructive interference in nonlinear network configurations, and (iv) controlling phase modulation in closed loop configurations. Though these results are obtained for simple model systems, the physics thus derived provides insights into the working of light harvesting systems, and the approaches thus developed apply to large-scale computation.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Electrons*
  • Energy Transfer*
  • Kinetics
  • Linear Models
  • Nonlinear Dynamics
  • Quantum Theory