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Article Dans Une Revue Journal of Computational Chemistry Année : 2020

An electron density based analysis to establish the electronic adiabaticity of proton coupled electron transfer reactions

Maria Gabriella Chiariello
  • Fonction : Auteur
| Federico Coppola
  • Fonction : Auteur
Fulvio Perrella
  • Fonction : Auteur
Marika Savarese
Umberto Raucci
  • Fonction : Auteur
  • PersonId : 1073775
Nadia Rega
  • Fonction : Auteur
  • PersonId : 1073776

Résumé

Electrons and protons are the main actors in play in proton coupled electron transfer (PCET) reactions, which are fundamental in many biological (i.e., photosynthesis and enzymatic reactions) and electrochemical processes. The mechanism, energetics and kinetics of PCET reactions are strongly controlled by the coupling between the transferred electrons and protons. Concerted PCET reactions are classified according to the electronical adiabaticity degree of the process. To discriminate among different mechanisms, we propose a new analysis based on the use of electron density based indexes. We choose, as test case, the 3-Methylphenoxyl/phenol system in two different conformations to show how the proposed analysis is a suitable tool to discriminate between the different degree of adiabaticity of PCET processes. The very low computational cost of this procedure is extremely promising to analyze and provide evidences of PCET mechanisms ruling the reactivity of many biological and catalytic systems. K E Y W O R D S density based indexes, density functional theory, electronic adiabaticity degree, non adiabatic coupling, proton coupled electron transfer
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Dates et versions

hal-02879687 , version 1 (12-11-2020)

Identifiants

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Ilaria Ciofini, Maria Gabriella Chiariello, | Federico Coppola, Fulvio Perrella, Marika Savarese, et al.. An electron density based analysis to establish the electronic adiabaticity of proton coupled electron transfer reactions. Journal of Computational Chemistry, 2020, ⟨10.1002/jcc.26224⟩. ⟨hal-02879687⟩
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