Machine learning-aided first-principles calculations of redox potentials

Author(s)
Ryosuke Jinnouchi, Ferenc Karsai, Georg Kresse
Abstract

We present a method combining first-principles calculations and machine learning to predict the redox potentials of half-cell reactions on the absolute scale. By applying machine learning force fields for thermodynamic integration from the oxidized to the reduced state, we achieve efficient statistical sampling over a broad phase space. Furthermore, through thermodynamic integration from machine learning force fields to potentials of semi-local functionals, and from semi-local functionals to hybrid functionals using Δ-machine learning, we refine the free energy with high precision step-by-step. Utilizing a hybrid functional that includes 25% exact exchange (PBE0), this method predicts the redox potentials of the three redox couples, Fe3+/Fe2+, Cu2+/Cu+, and Ag2+/Ag+, to be 0.92, 0.26, and 1.99 V, respectively. These predictions are in good agreement with the best experimental estimates (0.77, 0.15, 1.98 V). This work demonstrates that machine-learned surrogate models provide a flexible framework for refining the accuracy of free energy from coarse approximation methods to precise electronic structure calculations, while also facilitating sufficient statistical sampling.

Organisation(s)
Computational Materials Physics
External organisation(s)
VASP Software GmbH, Toyota Central R&D Labs., Inc.
Journal
npj Computational Materials
Volume
10
No. of pages
11
ISSN
2096-5001
DOI
https://doi.org/10.48550/arXiv.2309.13217
Publication date
05-2024
Peer reviewed
Yes
Austrian Fields of Science 2012
104022 Theoretical chemistry, 104005 Electrochemistry, 103043 Computational physics
ASJC Scopus subject areas
Modelling and Simulation, General Materials Science, Mechanics of Materials, Computer Science Applications
Portal url
https://ucrisportal.univie.ac.at/en/publications/60e6b754-22cb-47b6-bdb3-20513352c3ca