Reorganization energy of electron transfer in viscous solvents above the glass transition

Pradip K. Ghorai, Dmitry Matyushov

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12 Scopus citations

Abstract

We present a molecular-dynamics study of the solvent reorganization energy of electron transfer in supercooled water. 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. Both the heat capacity and dielectric susceptibility of the pure water show sharp drops at about the same temperature. 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 Debye relaxation of the solvent dipolar polarization.

Original languageEnglish (US)
Pages (from-to)1866-1871
Number of pages6
JournalJournal of Physical Chemistry B
Volume110
Issue number4
DOIs
StatePublished - Feb 2 2006

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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