Absolute standard hydrogen electrode potential and redox potentials of atoms and molecules: machine learning aided first principles calculations

Autor(en)

Ryosuke Jinnouchi, Ferenc Karsai, Georg Kresse

Abstrakt

Constructing a self-consistent first-principles framework that accurately predicts the properties of electron transfer reactions through finite-temperature molecular dynamics simulations is a dream of theoretical electrochemists and physical chemists. Yet, predicting even the absolute standard hydrogen electrode potential, the most fundamental reference for electrode potentials, proves to be extremely challenging. Here, we show that a hybrid functional incorporating 25% exact exchange enables quantitative predictions when statistically accurate phase-space sampling is achieved via thermodynamic integrations and thermodynamic perturbation theory calculations, utilizing machine-learned force fields and Δ-machine learning models. The application to seven redox couples, including molecules and transition metal ions, demonstrates that the hybrid functional can predict redox potentials across a wide range of potentials with an average error of 140 mV.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Toyota Central R&D Labs., Inc., VASP Software GmbH

Journal

Chemical Science

Anzahl der Seiten

9

ISSN

2041-6520

DOI

https://doi.org/10.48550/arXiv.2409.11000

Publikationsdatum

12-2024

Peer-reviewed

Ja

ÖFOS 2012

103006 Chemische Physik, 103043 Computational Physics

ASJC Scopus Sachgebiete

Allgemeine Chemie

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/4e87495e-cc8f-40d2-909b-c96290de86aa