Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I : General Formulation and Proton-coupled Electron Transfer Reactions
Melander, M. M. (2020). Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I : General Formulation and Proton-coupled Electron Transfer Reactions. Journal of the Electrochemical Society, 167(11), Article 116518. https://doi.org/10.1149/1945-7111/aba54b
Julkaistu sarjassa
Journal of the Electrochemical SocietyTekijät
Päivämäärä
2020Tekijänoikeudet
© 2020 Electrochemical Society
Electrochemical interfaces present a serious challenge for atomistic modelling. Electrochemical thermodynamics are naturally addressed within the grand canonical ensemble (GCE) but the lack of a fixed potential rate theory impedes fundamental understanding and computation of electrochemical rate constants. Herein, a generally valid electrochemical rate theory is developed by extending equilibrium canonical rate theory to the GCE. The extension provides a rigorous framework for addressing classical reactions, nuclear tunneling and other quantum effects, non-adiabaticity etc. from a single unified theoretical framework. The rate expressions can be parametrized directly with self-consistent GCE-DFT methods. These features enable a well-defined first principles route to addressing reaction barriers and prefactors (proton-coupled) electron transfer reactions at fixed potentials. Specific rate equations are derived for adiabatic classical transition state theory and adiabatic GCE empirical valence bond (GCE-EVB) theory resulting in a Marcus-like expression within GCE. From GCE-EVB general free energy relations for electrochemical systems are derived. The GCE-EVB theory is demonstrated by predicting the PCET rates and transition state geometries for the adiabatic Au-catalyzed acidic Volmer reaction using (constrained) GCE-DFT. The work herein provides the theoretical basis and practical computational approaches to electrochemical rates with numerous applications in physical and computational electrochemistry.
...
Julkaisija
Electrochemical SocietyISSN Hae Julkaisufoorumista
0013-4651Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/42677197
Metadata
Näytä kaikki kuvailutiedotKokoelmat
Lisenssi
Samankaltainen aineisto
Näytetään aineistoja, joilla on samankaltainen nimeke tai asiasanat.
-
Grand canonical ensemble approach to electrochemical thermodynamics, kinetics, and model Hamiltonians
Melander, Marko M. (Elsevier, 2021)The unique feature of electrochemistry is the ability to control reaction thermodynamics and kinetics by the application of electrode potential. Recently, theoretical methods and computational approaches within the grand ... -
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and electrode potentials
Melander, Marko; Kuisma, Mikael; Christensen, Thorbjørn Erik Køppen; Honkala, Karoliina (AIP Publishing LLC, 2019)Properties of solid-liquid interfaces are of immense importance for electrocatalytic and electrochemical systems, but modeling such interfaces at the atomic level presents a serious challenge and approaches beyond standard ... -
Frozen or dynamic? : An atomistic simulation perspective on the timescales of electrochemical reactions
Melander, Marko M. (Elsevier BV, 2023)Electrochemical systems span a wide range of timescales, and several recent works have put forth the idea that the reaction environment should remain frozen and out of equilibrium during electrochemical electron or proton ... -
2023 Roadmap on molecular modelling of electrochemical energy materials
Zhang, Chao; Cheng, Jun; Chen, Yiming; Chan, Maria K. Y.; Cai, Qiong; Carvalho, Rodrigo P.; Marchiori, Cleber F. N.; Brandell, Daniel; Araujo, C. Moyses; Chen, Ming; Ji, Xiangyu; Feng, Guang; Goloviznina, Kateryna; Serva, Alessandra; Salanne, Mathieu; Mandai, Toshihiko; Hosaka, Tomooki; Alhanash, Mirna; Johansson, Patrik; Qiu, Yun-Ze; Xiao, Hai; Eikerling, Michael; Jinnouchi, Ryosuke; Melander, Marko M.; Kastlunger, Georg; Bouzid, Assil; Pasquarello, Alfredo; Shin, Seung-Jae; Kim, Minho M.; Kim, Hyungjun; Schwarz, Kathleen; Sundararaman, Ravishankar (IOP Publishing, 2023)New materials for electrochemical energy storage and conversion are the key to the electrification and sustainable development of our modern societies. Molecular modelling based on the principles of quantum mechanics and ... -
Grand Canonical DFT Investigation of the CO2RR and HER Reaction Mechanisms on MoTe2 Edges
Pedersen, Pernille D.; Melander, Marko M.; Bligaard, Thomas; Vegge, Tejs; Honkala, Karoliina; Hansen, Heine A. (American Chemical Society (ACS), 2023)MoTe2 has been experimentally and theoretically identified as a promising cathode candidate for electrocatalytic CO2 reduction (CO2RR). A full understanding of its reactivity requires special consideration of the reaction ...
Ellei toisin mainittu, julkisesti saatavilla olevia JYX-metatietoja (poislukien tiivistelmät) saa vapaasti uudelleenkäyttää CC0-lisenssillä.