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NN potentials map gold–water ORR paths

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Equivariant neural-network potentials drive nanosecond metadynamics showing associative ORR on Au(100) in which *OOH is reduced to two *OH, with a ~0.3 eV barrier.

Source

Neural network potentials for accelerated metadynamics of oxygen reduction kinetics at Au-water interfaces

Yang X, Bhowmik A, Vegge T, et al. · Chemical science · 2023

doi.org/10.1039/d2sc06696cRead the full paper ↗29 citationscc by

Study at a glance

Design
Computational / modelling — PaiNN active-learning NNPs enabling path-CV metadynamics of ORR on Au(100)–water
N
2.5 ns production metadynamics after AIMD active learning — no sample N
Population
Au(100)–water models with O2/OH adsorbates
Outcome
Associative ORR pathway and ~0.3 eV O2-to-hydroxyl barrier

Structured fields used in claim comparison tables when every cited study has a complete layer.

What they did

They trained a PaiNN ensemble on DFT (PBE-D3) data selected by CUR active learning from AIMD of Au(100)–water with O2 and OH adsorbates, then ran 2.5 ns path-CV metadynamics in water at 350 K. Path collective variables tracked O–O and O–H coordination so the reduction path did not have to be guessed in advance.

What they found

ORR follows an associative path: O2 is hydrogenated toward *OOH, which is reduced to two *OH with neighboring water rather than splitting into *OH + *O. The O2-to-hydroxyl barrier is about 0.3 eV, matching gold’s high experimental ORR activity. Active learning continued until MD could run beyond 5 ns without large force uncertainty.

The limits

What it doesn't show

The model is Au(100) in pure water without explicit cations or applied potential as in alkaline ORR cells. Facet dependence is left for future work. The 0.3 eV barrier is from the NNP/MetaD landscape, not a measured Tafel slope on the same electrode.

Key terms

Oxygen reduction reaction (ORR)
Electrochemical conversion of O2 to water or hydroxide, the cathode reaction in many fuel cells.
Neural network potential
ML model that predicts energies/forces near DFT cost at MD speed.
Metadynamics
Enhanced sampling that adds a history-dependent bias along collective variables to cross barriers.
Associative ORR path
O2 is hydrogenated to *OOH before O–O cleavage, rather than dissociating first.
PaiNN
Polarizable equivariant message-passing neural network used as the potential here.

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The simulated electrode is:

Common questions

Why not just run AIMD for ORR?

AIMD is too short (picoseconds) to equilibrate water and sample rare ORR events; NNPs reach nanoseconds.

Does *OOH split into *O and *OH?

Not in these trajectories—neighboring water helps reduce *OOH to two *OH.

What barrier did they estimate?

About 0.3 eV from O2 to hydroxyls.

Which gold face was modeled?

Au(100) with explicit water.

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