| Full text | |
| Author(s): |
Bueno, Paulo Roberto
Total Authors: 1
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| Document type: | Journal article |
| Source: | Electrochimica Acta; v. 466, p. 18-pg., 2023-08-17. |
| Abstract | |
Quantum rate theory is based on a first-principle quantum mechanical rate concept that comprises with the Planck-Einstein relationship E = hv, where v = e(2)/hC(q) is a frequency associated with the quantum capacitance C-q and E = e(2)/C-q is the energy associated with v. For a single state mode of transmittance, e(2)/C-q corresponds to the chemical potential differences Delta mu between donor and acceptor state levels comprising an electrochemical reaction. A statistical mechanic treatment of E is required to compute the contribution of the thermal dynamics at finite temperature. The Arrhenius equation for the temperature dependence of the reaction rate was obtained, as well as Marcus's Arrhenius-type electron-transfer rate constant as a particular setting of the quantum rate v. Consequently, this v concept provides the quantum mechanical foundations for electrochemical reactions at room temperature. The present work also demonstrates that the electron-transfer rate of heterogeneous (diffusionless) reactions can be studied in detail within this theory by measuring C-q using time-dependent electrochemical methods. Since the electron transfer follows a statistical mechanics version of the Planck-Einstein E = hv relationship, the electrochemical reaction dynamics cannot be appropriately modeled using non-relativistic Schrodinger wave mechanics, which is the ongoing quantum approach to electrochemistry. Accordingly, a relativistic analysis that takes into account the spin dynamics of the electron is more appropriate. The latter assumption implies quantum electrodynamics within a particular quantum transport mode intrinsically coupled to the electron-transfer rate of electrochemical reactions that have not been considered thus far. Here it is demonstrated that the consideration of this inherent quantum transport is key to obtaining an in-depth understanding of the electron transfer phenomenon. Finally, the theory is validated through its description of electron transfer, quantum conductance, and capacitance in different electro-active molecular films. (AU) | |
| FAPESP's process: | 17/24839-0 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications |
| Grantee: | Paulo Roberto Bueno |
| Support Opportunities: | Research Projects - Thematic Grants |