Reorganization energy of electron transfer in polar liquids. Dependence on reactant size, temperature and pressure

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77 Citations (Scopus)

Abstract

The solvent reorganization energy of outer sphere electron transfer in polar liquids is derived in a molecular treatment. The reorganization energy is shown to be the sum of two contributions: the reorganization energy of reorientation of liquid permanent dipoles and and the energy of reorganization of the liquid density. Reorientation of the dipoles gives the main contribution to the solvent reorganization energy, whereas reorganization of the density contributes mainly to the activation entropy which is positive in the normal and negative in the inverted regions of electron transfer. The reorganization energy of the liquid density contains an explicit temperature dependence which causes the non-Arrhenius temperature dependence of the rate constant. Entropy, enthalpy and volume of activation are found for several solvents.

Original languageEnglish (US)
Pages (from-to)199-218
Number of pages20
JournalChemical Physics
Volume174
Issue number2
DOIs
StatePublished - Aug 1 1993
Externally publishedYes

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Density of liquids
electron transfer
Electrons
Liquids
Entropy
liquids
Chemical activation
Temperature
retraining
temperature
energy
Enthalpy
Rate constants
activation
entropy
dipoles
temperature dependence
enthalpy
causes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Reorganization energy of electron transfer in polar liquids. Dependence on reactant size, temperature and pressure. / Matyushov, Dmitry.

In: Chemical Physics, Vol. 174, No. 2, 01.08.1993, p. 199-218.

Research output: Contribution to journalArticle

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