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Modeling of electron transfer across electrochemical interfaces: State‐of‐the art and challenges for quantum and computational chemistry
Author(s) -
Nazmutdinov Renat R.,
Bronshtein Michael D.,
Zinkicheva Tamara T.,
Glukhov Dmitrii V.
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25035
Subject(s) - electron transfer , chemistry , charge transfer coefficient , redox , chemical physics , quantum , quantum chemistry , electrolyte , electrochemistry , electrocatalyst , reaction rate constant , electron , electrode , marcus theory , standard electrode potential , charge (physics) , work (physics) , computational chemistry , nanotechnology , thermodynamics , materials science , physics , quantum mechanics , kinetics , inorganic chemistry , cyclic voltammetry
State‐of‐the‐art in the area of quantum‐chemical modeling of electron transfer (ET) processes at metal electrode/electrolyte solution interfaces is reviewed. Emphasis is put on key quantities which control the ET rate (activation energy, transmission coefficient, and work terms). Orbital overlap effect in electrocatalysis is thoroughly discussed. The advantages and drawbacks of cluster and periodical slab models for a metal electrode when describing redox processes are analyzed as well. It is stressed that reliable quantitative estimations of the rate constants of interfacial charge transfer reactions are hardly possible, while predictions of qualitatively interesting effects are more valuable. © 2015 Wiley Periodicals, Inc.