An electron density based analysis to establish the electronic adiabaticity of proton coupled electron transfer reactions |
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Authors: | Umberto Raucci Maria Gabriella Chiariello Federico Coppola Fulvio Perrella Marika Savarese Ilaria Ciofini Nadia Rega |
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Affiliation: | 1. Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario di M.S.Angelo, Napoli, Italy;2. CompuNet, Istituto Italiano di Tecnologia, Genoa, Italy;3. Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, Paris, France |
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Abstract: | 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. |
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Keywords: | density based indexes density functional theory electronic adiabaticity degree non adiabatic coupling proton coupled electron transfer |
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