Half Reactions with Multiple Redox States Do Not Follow the Standard Theory: A Computational Study of Electrochemistry of C60

Setare Mostajabi Sarhangi, Morteza M. Waskasi, Seyed Majid Hashemianzadeh, Daniel R. Martin, Dmitry Matyushov

Research output: Contribution to journalArticle

2 Scopus citations

Abstract

The standard theory of electron transfer advanced by Marcus suggests that the solvent reorganization energy does not depend on the redox state of the reactant. This theory prediction is verifiable by measuring activation barriers of electron transfer reactions involving multiple oxidation states. We use here the opportunity offered by electrochemistry of C60, which allows charges from zero to negative four in a sequence of reduction half reactions. We find that the activation barrier does change with altering redox state of fullerene, which can be experimentally verified by measuring Arrhenius slopes of corresponding reaction rates. This outcome is connected to the alteration of the molecular polarizability caused by electronic transitions. Classical molecular dynamics simulations of fullerene in water are combined here with the analytical Q-model of electron transfer involving polarizable molecules. The main outcome of the study is that altering molecular polarizability makes the reorganization energy and the reaction activation barrier depend on the redox state of the reactant.

Original languageEnglish (US)
JournalJournal of Physical Chemistry C
DOIs
StateAccepted/In press - May 18 2018

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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