Nuclear quantum effects of metal surface-mediated C–H activation

Bunting, Rhys J.; Shepherd, Sam; Rampal, Nikhil; Akhade, Sneha; Wilkins, David M.; Pham, Tuan Anh

doi:10.1039/D5CP01527H

Nuclear quantum effects of metal surface-mediated C–H activation

Journal Article · Mon Jul 14 00:00:00 EDT 2025 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D5CP01527H· OSTI ID:2585272

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Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Queen's Univ., Belfast, Northern Ireland (United Kingdom)

The nuclear quantum effects of surface-mediated C–H activation of surface CH₃ are considered for the pristine Pt(111) and Au(111) surfaces at 300 K. The kinetic barriers without nuclear quantum effects are calculated using both static density functional theory calculations and ab initio molecular dynamics. Static calculations are performed using the harmonic approximation while the free energy pathway is calculated using enhanced sampling molecular dynamics. Machine learning potentials are trained using generated datasets and validated against the ab initio molecular dynamics generated free energy pathways. The machine learning potentials are used to perform centroid molecular dynamics to consider the nuclear quantum effects of C–H activation. Nuclear quantum effects are found to have a very significant effect on the free energy pathway, with reduced importance at higher temperatures and in the CD₃ case.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2585272

Report Number(s):: LLNL--JRNL-2000762

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 30 Vol. 27; ISSN 1463-9076; ISSN 1463-9084

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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