Theoretical studies of proton-coupled electron transfer: Models and concepts relevant to bioenergetics

Sharon Hammes-Schiffer, Elizabeth Hatcher, Hiroshi Ishikita, Jonathan H. Skone, Alexander V. Soudackov

Research output: Contribution to journalReview articlepeer-review

80 Scopus citations


Theoretical studies of proton-coupled electron transfer (PCET) reactions for model systems provide insight into fundamental concepts relevant to bioenergetics. A dynamical theoretical formulation for vibronically nonadiabatic PCET reactions has been developed. This theory enables the calculation of rates and kinetic isotope effects, as well as the pH and temperature dependences, of PCET reactions. Methods for calculating the vibronic couplings for PCET systems have also been developed and implemented. These theoretical approaches have been applied to a wide range of PCET reactions, including tyrosyl radical generation in a tyrosine-bound rhenium polypyridyl complex, phenoxyl/phenol and benzyl/toluene self-exchange reactions, and hydrogen abstraction catalyzed by the enzyme lipoxygenase. These applications have elucidated some of the key underlying physical principles of PCET reactions. The tools and concepts derived from these theoretical studies provide the foundation for future theoretical studies of PCET in more complex bioenergetic systems such as Photosystem II.

Original languageEnglish (US)
Pages (from-to)384-394
Number of pages11
JournalCoordination Chemistry Reviews
Issue number3-4
StatePublished - Feb 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


  • Electron transfer
  • Hydrogen transfer
  • Proton transfer
  • Proton-coupled electron transfer


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