Influence of environment and intramolecular vibrations on the kinetics of occupancy of the triplet state of the donor molecule

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Within the framework of the stochastic approach, a numerical study of the kinetics of occupancy of the triplet state of an electron donor molecule caused by photoinduced electron transfer from the donor to the paramagnetic acceptor and back is performed. The conditions are determined, and a general strategy for achieving the maximum efficiency of triplet molecule accumulation induced by the electron transfer is stated. Solvents with fast dielectric relaxation are shown to contribute to increasing the efficiency of the process involved.

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Sobre autores

E. Minakova

Volgograd State University

Email: mikhailova.va@volsu.ru
Rússia, Volgograd

E. Mikhailova

Volgograd State University

Email: mikhailova.va@volsu.ru
Rússia, Volgograd

V. Mikhailova

Volgograd State University

Autor responsável pela correspondência
Email: mikhailova.va@volsu.ru
Rússia, Volgograd

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2. Fig. 1. Profiles of the Gibbs free energy surfaces (FES) along the reaction coordinate Q. The dotted lines show vibrationally excited states (only one IMC mode with frequency Ωα is excited). Relaxations of the solvent and vibrations are schematically shown by arrows.

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3. Fig. 2. Population kinetics Ps(s = 1, 2, 3) at different values ​​of │∆G12│ (values ​​are indicated in eV as the argument Ps.).

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4. Fig. 3. Dependences of the effective rate constant of PE on the paramagnetic center k12 on |∆G12| for different values ​​of Erv (values ​​in eV are indicated next to the curves on the left) and τ2 (values ​​in ps are indicated next to the curves on the right).

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5. Fig. 4. k23 dependences on |∆G23|. Calculated parameters: a) 0 – line – without IMC; 1 – 1 IMC with effective frequency Ω1 = 0.17 eV is excited, 2 and 3 – 5 oscillations are excited, parameters Erv (in eV), Δ23 (in eV) are indicated near the curves; b) the values ​​of τ2 (in ps) are indicated next to the curves, Erv = 0.2 eV, Erm = 0.4 eV, V12 = 0.03 eV, ∆12 = 0.04 eV.

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6. Fig. 5. Dependences of  (a) and  (b) on τ2 for different values ​​of │∆G12│ and │∆G23│ (the values ​​are given next to the curves in eV). Calculated parametersErv = 0.2 eV, Erm = 0.4 eV, V12 = 0.03 eV, ∆12 = 0.04 eV.

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7. Fig. 6. Dependences of k23 on ∆23 for different values ​​of │∆G23│ (shown next to the curves in eV). Calculated parametersErv = 0.2 eV, Erm = 0.4 eV, V12 = 0.03 eV, τ2 = 1.52 ps (solid), 3.52 ps (dashed).

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