Modeling of ultrafast electron-transfer processes: Validity of multilevel Redfield theory

Abstract

Articles you may be interested inThree-centered model of ultrafast photoinduced charge transfer: Continuum dielectric approach A perturbation molecular orbital theory of electron-transfer ratesThe capability of multilevel Redfield theory to describe ultrafast photoinduced electron-transfer reactions is investigated. Adopting a standard model of photoinduced electron transfer in a condensed-phase environment, we consider electron-transfer reactions in the normal and inverted regimes, as well as for different values of the electron-transfer parameters, such as reorganization energy, electronic coupling, and temperature. Based on the comparison with numerically exact reference results, obtained using the self-consistent hybrid method, we discuss in some detail the advantages and shortcomings of two different versions of Redfield theory, which employ the time-dependent and stationary Redfield tensor, respectively. The results of the study demonstrate that multilevel Redfield theory, if applied in the appropriate parameter regime, is well suited to describe the ultrafast coherent dynamics of photoinduced electron-transfer reactions.

Theory of ultrafast photoinduced heterogeneous electron transfer

“…[6][7][8] for the early contributions and, e.g., Refs. [9][10][11][12][13] for some recent activities).…”

Formation of nonequilibrium steady states in interacting double quantum dots: When coherences dominate the charge distribution

“…This behavior is due to the shift of the integration limit in Eq. (20) and has been outlined before by Thoss et al [52,127].…”

“…Due to the approximations involved, the master equation (20) describes a non-unitary time evolution of the reduced density matrix, which can result in unphysical negative populations [52,53]. This problem can be avoided by shifting the integration limit t to ∞ and, at the same time, neglecting principal value terms that arise in the evaluation of the resulting integrals.…”

“…equations [3,52,[115][116][117]. Note that neither the HQME (in particular our truncation scheme [43]) nor the BM formalism depends on the choice of the basis.…”

“…This deficiency in the literature can be traced back to the limitations of many time-dependent methods which involve approximations (giving, e.g., unphysical populations [52,53] and currents [43]), impose severe restrictions on the accessible time scales [54][55][56][57][58][59][60][61][62][63][64][65] or enable study only of parts of the full parameter space [43,54,55,58,63,[66][67][68].…”