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Molecular Simulations of Outersphere Reorganization Energies in Polar and Quadrupolar Solvents. The Case of Intramolecular Electron and Hole Transferстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 8 сентября 2021 г.
- Авторы: Vener M.V., Tovmash A.V., Rostov I.V., Basilevsky M.V.
- Журнал: Journal of Physical Chemistry B
- Том: 110
- Номер: 30
- Год издания: 2006
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 14950
- Последняя страница: 14955
- DOI: 10.1021/jp061069h
- Аннотация: Outersphere reorganization energies (λ) for intramolecular electron and hole transfer are studied in anion- and cation-radical forms of complex organic substrates (p-phenylphenyl-spacer-naphthyl) in polar (water, 1,2-dichloroethane, tetrahydrofuran) and quadrupolar (supercritical CO2) solvents. Structure and charge distributions of solute molecules are obtained at the HF/6-31G(d,p) level. Standard Lennard-Jones parameters for solutes and the nonpolarizable simple site-based models of solvents are used in molecular dynamics (MD) simulations. Calculation of λ is done by means of the original procedure, which treats electrostatic polarization of a solvent in terms of a usual nonpolarizable MD scheme supplemented by scaling of reorganization energies at the final stage. This approach provides a physically relevant background for separating inertial and inertialless polarization responses by means of a single parameter ε∞, optical dielectric permittivity of the solvent. Absolute λ values for hole transfer in 1,2-dichloroethane agree with results of previous computations in terms of the different technique (MD/FRCM, Leontyev, I. V.; et al. Chem. Phys. 2005, 319, 4). Computed λ values for electron transfer in tetrahydrofuran are larger than the experimental values by ca. 2.5 kcal/mol; for the case of hole transfer in 1,2-dichloroethane the discrepancy is of similar magnitude provided the experimental data are properly corrected. The MD approach gives nonzero λ values for charge-transfer reaction in supercritical CO2, being able to provide a uniform treatment of nonequilibrium solvation phenomena in both quadrupolar and polar solvents.
- Добавил в систему: Венер Михаил Владимирович