Modeling of electron transfer across electrochemical interfaces: State-of-the art and challenges for quantum and computational chemistry

• Published in: International journal of quantum chemistry 2016-02, Vol.116 (3), p.189-201
• Main Authors: Nazmutdinov, Renat R., Bronshtein, Michael D., Zinkicheva, Tamara T., Glukhov, Dmitrii V.
• Format: Article
• Language: English
• Subjects: Chemistry; density functional theory; electron transfer; electronic transmission coefficient; metal/electrolyte solution interface; Physical chemistry; Quantum physics; reaction free energy surfaces
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.25035

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. Electron transfer reactions play an exceedingly important role in our life. Such chemical reactions occurring at multifarious electrochemical interfaces can be regarded as the most complicated. To understand some exciting features of redox processes observed in experiment, as well as to control electron transfer in a proper way, one needs a molecular level insight into the elementary act. This can be attained in the framework of a rigorous quantum mechanical theory combined with the power of modern computational chemistry. In this article we discuss the most interesting model approaches which are bridging theoretical predictions with experiment. For quantum chemistry, on the other hand, the realm of various redox reactions remains tour de force and prompts the further development of computational methods.