Solvent reorganization of electron transitions in viscous solvents

The Journal of Chemical Physics
Pradip K Ghorai, Dmitry V Matyushov

Abstract

We develop a model of electron transfer reactions at conditions of nonergodicity when the time of solvent relaxation crosses the observation time window set up by the reaction rate. Solvent reorganization energy of intramolecular electron transfer in a charge-transfer molecule dissolved in water and acetonitrile is studied by molecular dynamics simulations at varying temperatures. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect, as discussed by the mode-coupling theory. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the breakdown of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to the relaxation of the solvent dipolar polarization. An analytical theory proposed to describe this effect agrees well with both the simulations and experimental Stokes shift data. The theory is applied to the analysis of charge-transfer kinetics in a low-temperature glass former. We show that the reorganization energy is substantially low...Continue Reading

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Citations

May 2, 2009·The Journal of Chemical Physics·Dmitry V Matyushov
Jan 21, 2014·The Journal of Chemical Physics·Mehdi ZareaMichael R Wasielewski
Jul 20, 2006·The Journal of Chemical Physics·Naoki ItoRanko Richert
Feb 23, 2008·Physical Chemistry Chemical Physics : PCCP·Mark A BergCatherine J Murphy
Nov 23, 2017·The Journal of Chemical Physics·Dmitry V Matyushov, Marshall D Newton
Apr 14, 2020·The Journal of Physical Chemistry. B·Pradip Kumar Ghorai, Dmitry V Matyushov
Mar 5, 2009·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·David N Lebard, Dmitry V Matyushov
Jul 19, 2008·The Journal of Physical Chemistry. B·David N LeBardDmitry V Matyushov
Aug 21, 2009·The Journal of Physical Chemistry. B·David N Lebard, Dmitry V Matyushov
Nov 3, 2017·Journal of Chemical Theory and Computation·Subhajyoti ChaudhuriVictor S Batista
Nov 10, 2018·Journal of the American Chemical Society·Shahnawaz Rafiq, Gregory D Scholes
Mar 18, 2008·The Journal of Physical Chemistry. B·David N LeBard, Dmitry V Matyushov
Jun 30, 2006·The Journal of Physical Chemistry. B·Vitaliy Kapko, Dmitry V Matyushov

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