(Color) Potential-energy curves (red) and (blue) of the (a) Morse and the (b) harmonic electron-transfer models. The red and blue lines indicate the eigenstates pertaining predominantly to the electronic states and , respectively. The arrows between the lines illustrate the allowed vibrational transitions of the system. Here, the black arrows refer to the vibrational transitions in a single diabatic electronic state, while magenta and green arrows refer to the vibrational transitions between the two coupled electronic states and .
(Color) Electronic and vibrational relaxation dynamics of the anharmonic electron-transfer model as exhibited by (a) the population probability of the initially excited electronic state and (b) the mean position of the Morse oscillator. Compared are results obtained for the undamped system (red) as well as for the damped system calculated from the Redfield formulation, with (green) and without (blue) using the secular approximation. The vibrational energy relaxation of the damped system is characterized by the Redfield results of the mean vibrational level number and its standard deviation (dashed line) shown in panel (c).
(Color) Cuts of the vis/IR pump-probe spectrum for the anharmonic electron-transfer model, obtained for delay times (black), (red), (green), (blue), and (cyan). Shown are the (a) absorption, (b) emission, (c) total spectrum, and (d) difference spectrum.
(Color) As in Fig. 3, but for the adiabatic electron-transfer model, i.e., in the absence of vibronic coupling .
(Color) As in Fig. 2, but for the harmonic electron-transfer model.
(Color) As in Fig. 3, but for the harmonic electron-transfer model.
Frequencies (in ) of the allowed vibrational transitions between eigenstates and , as obtained for the harmonic and Morse electron-transfer models, respectively. The first two sets of transitions take place in a single diabatic electronic state, or . The other two sets take place between the two coupled electronic states , where the ± indicates that the corresponding transitions are shifted by approximately .
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