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An electron density based analysis to establish the electronic adiabaticity of proton coupled electron transfer reactions
Author(s) -
Raucci Umberto,
Chiariello Maria Gabriella,
Coppola Federico,
Perrella Fulvio,
Savarese Marika,
Ciofini Ilaria,
Rega Nadia
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26224
Subject(s) - proton coupled electron transfer , electron transfer , proton , electron , chemical physics , chemistry , reactivity (psychology) , density functional theory , computational chemistry , atomic physics , photochemistry , physics , quantum mechanics , medicine , alternative medicine , pathology
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.