Abstract
The standard oxidation potential and the electron transfer (ET) rate constants of two silicon-based hybrid interfaces, Si(111)/organic-spacer/Ferrocene, are theoretically calculated and assessed. The dynamics of the electrochemical driven ET process is modeled in terms of the classical donor/acceptor scheme within the framework of “Marcus theory”. The ET rate constants, , are determined following calculation of the electron transfer matrix element, , together with the knowledge of the energy of the neutral and charge separated systems. The recently introduced Constrained Density Functional Theory (CDFT) method is exploited to optimize the structure and determine the energy of the charge separated species. Calculated ET rate constants are and , in the case of the short and long organic-spacer, respectively.
Highlights
Beyond any possible doubt, Silicon is a fundamental material of utmost importance for both applicative purposes and pure science [1]
Different methodologies exist for the preparation of hybrid silicon-based interfaces, relying on the covalent grafting of organic molecules, and these are generally based on ultra-high vacuum (UHV) depositions [7,8,9], wet chemistry exploiting UV curing [10,11], electrochemical-based methodologies [12,13]
∆Ereact isOxidation the difference in energy between the reagents and the products, i.e., the thermodynamic electrochemical behavior of the chemi-adsorbed ferrocene is assumed as a reversible single-step single-electron oxidation process, Scheme 2, where IP is the ionization potential and
Summary
Department of Engineering “Enzo Ferrari”, DIEF, University of Modena and Reggio Emilia, via Vivarelli 10, 41125 Modena, Italy Department of Chemistry, University of Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Italy; Received: 5 August 2017; Accepted: 18 September 2017; Published: 21 September 2017
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