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Proton-coupled electron transfer in solution, proteins, and electrochemistry.

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Recent theoretical advances unify the treatment of proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) reactions. A new diagnostic distinguishes HAT from PCET based on electronic nonadiabaticity, crucial for understanding energy conversion and biological processes.

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Area of Science:

  • Physical Chemistry
  • Theoretical Chemistry
  • Chemical Dynamics

Background:

  • Proton-coupled electron transfer (PCET) reactions are vital in biological systems and energy technologies like fuel and solar cells.
  • Understanding the mechanisms of PCET and hydrogen atom transfer (HAT) is crucial for optimizing these processes.

Purpose of the Study:

  • To review recent theoretical advancements in treating PCET reactions.
  • To present a unified theoretical framework for sequential and concerted PCET, and HAT.
  • To introduce a quantitative method for differentiating between HAT and PCET.

Main Methods:

  • Development of a unified theoretical framework for PCET and HAT.
  • Proposal of a quantitative diagnostic based on electronic nonadiabaticity to distinguish HAT from PCET.
  • Derivation of rate constant expressions considering solvent response and vibrational motion.
  • Application of theoretical treatments to solution and protein environments, including explicit molecular dynamics.

Main Results:

  • A unified theory now describes sequential PCET, concerted PCET, and HAT.
  • A diagnostic tool differentiates HAT (electronically adiabatic proton transfer) from PCET (electronically nonadiabatic proton transfer).
  • Rate constant expressions were derived, accounting for solvent and vibrational effects.
  • Theoretical models were successfully applied to various PCET systems in solution and proteins.

Conclusions:

  • The developed theoretical framework provides a comprehensive understanding of PCET and HAT mechanisms.
  • The electronic nonadiabaticity diagnostic offers a clear distinction between these reaction types.
  • The derived rate expressions are applicable to diverse chemical and biological systems, including electrochemical applications.