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

Journal: Physical chemistry chemical physics : PCCP
Published Date: Jul 30, 2025

Abstract

The nuclear quantum effects of surface-mediated C-H activation of surface CH 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 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 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 CD case.

Authors

  • Rhys J Bunting
    Quantum Simulations Group, Materials Science Division and Laboratory for Energy Applications for the Future, Lawrence Livermore National Laboratory, Livermore, California 94550, USA. pham16@llnl.gov.
  • Sam Shepherd
    Centre for Quantum Materials and Technologies, School of Mathematics and Physics, Queens University Belfast, Belfast BT7 1NN, Northern Ireland, UK. d.wilkins@qub.ac.uk.
  • Nikhil Rampal
    Quantum Simulations Group, Materials Science Division and Laboratory for Energy Applications for the Future, Lawrence Livermore National Laboratory, Livermore, California 94550, USA. pham16@llnl.gov.
  • Sneha Akhade
    Quantum Simulations Group, Materials Science Division and Laboratory for Energy Applications for the Future, Lawrence Livermore National Laboratory, Livermore, California 94550, USA. pham16@llnl.gov.
  • David M Wilkins
    Laboratory of Computational Science and Modeling, IMX, École Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
  • Tuan Anh Pham
    University of Transport Technology, Hanoi, Vietnam.

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