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On the adequacy of the Redfield equation and related approaches to the study of quantum dynamics in electronic energy transfer
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View: Figures


Image of FIG. 1.
FIG. 1.

Intersite energy transfer rates from to , , as a function of the reorganization energy, , predicted by the full-Redfield equation (open circles), the secular-Redfield equation (open squares), and the nonsecular-Redfield equation without the imaginary parts of the relaxation tensors (open triangles). As a benchmark for a strong reorganization energy region, the rate calculated from Förster theory is also shown (solid line). The other parameters are , , , and . For these parameters, the intersite dynamics is dominantly incoherent for the entire region depicted and the positivity problem does not occur.

Image of FIG. 2.
FIG. 2.

Linear absorption spectrum for a monomer. In the left figure, the lower parabola is an electronic ground state while the upper parabola is an electronic excited state. The gray packets illustrate the phonon states in each electronic state. In the right graph, the solid line is obtained from the full-Redfield equation while the dashed line is calculated by disregarding the imaginary parts of the Redfield tensor. The parameters are set to be , , and . The frequency shift between the two spectra is identical to the reorganization energy, .

Image of FIG. 3.
FIG. 3.

Schematic of the EET mechanism of the full-Redfield equation (a) and Förster theory (b) in a region of large reorganization energy. In the full-Redfield equation (a), the phonons are always in equilibrium under the electron-phonon interaction due to the Markov approximation. Thus, the electronic de-excitation (down-pointing arrow) of site 1 and excitation (up-pointing arrow) of site 2 occur involving only the equilibrium phonon state. This process is independent of reorganization energy. On the other hand, in the Förster theory (b), the de-excitation and excitation occur from the equilibrium phonons of the initial state, , to the nonequilibrium phonons of the final state, , in accordance to the Franck–Condon principle. The nonequilibrium states are dependent on the magnitude of reorganization energy.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: On the adequacy of the Redfield equation and related approaches to the study of quantum dynamics in electronic energy transfer