Nonequilibrium generalization of Förster–Dexter theory for excitation energy transfer

Abstract

Förster-Dexter theory for excitation energy transfer is generalized for the account of short time nonequilibrium kinetics due to the nonstationary bath relaxation. The final rate expression is presented as a spectral overlap between the time dependent stimulated emission and the stationary absorption profiles, which allows experimental determination of the time dependent rate. For a harmonic oscillator bath model, an explicit rate expression is derived and model calculations are performed in order to examine the dependence of the nonequilibrium kinetics on the excitation-bath coupling strength and the temperature. Relevance of the present theory with recent experimental findings and possible future theoretical directions are discussed.

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

“…A testimonial to this are recent works attempting to improve their accuracy in various regimes of approximation [40][41][42][43][44][45][46]. Our effort, presented in this work, can be understood as an integral part of this trend.…”

Quantum Dynamics of Radiationless Electronic Transitions Including Normal Modes Displacements and Duschinsky Rotations: A Second-Order Cumulant Approach

“…The cumulant approach, [16][17][18][19][20][21][22] recently discussed and successfully applied to spin-boson and linear vibronic coupling Hamiltonian model, [23][24][25][26] allows to take into account the change of the reaction rate with time, describing the population P (t) of the state of interest with an equation of the form…”

A coherent modified Redfield theory for excitation energy transfer in molecular aggregates

“…Recently, Novoderezhkin and van Grondelle have comprehensively evaluated the validity of the modified Redfield theory by benchmarking it against other theoretical methods [28,4] and by applying it to fit experimental data [31,29,32]. They conclude that a combination of modified Redfield approach and generalized Förster theory [33] yields excellent simulations of EET dynamics in photosynthetic systems [32]. Despite its popularity in photosynthetic EET, the modified Redfield theory cannot be applied to model coherent EET since coherence dynamics are neglected fully.…”