Bond-selective effect for the dissociative chemisorption of HOD on the Ni(100) surface revealed at the full-dimensional quantum dynamical level

Tianhui Liu; Bina Fu; Dong H Zhang

doi:10.1063/5.0201925

Bond-selective effect for the dissociative chemisorption of HOD on the Ni(100) surface revealed at the full-dimensional quantum dynamical level

J Chem Phys. 2024 May 7;160(17):174303. doi: 10.1063/5.0201925.

Authors

Tianhui Liu^{1

2}, Bina Fu^{3

4

5}, Dong H Zhang^{3

4

5}

Affiliations

¹ School of Sciences, Great Bay University, Dongguan 523000, China.
² Great Bay Institute for Advanced Study, Dongguan 523000, China.
³ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁴ University of Chinese Academy of Sciences, Beijing 100049, China.
⁵ Hefei National Laboratory, Hefei 230088, China.

PMID: 38747993
DOI: 10.1063/5.0201925

Abstract

We present a comprehensive investigation into the dissociative chemisorption of HOD on a rigid Ni(100) surface using an approximate full-dimensional (9D) quantum dynamics approach, which was based on the time-dependent wave-packet calculations on a full-dimensional potential energy surface obtained through neural network fitting to density functional theory energy points. The approximate-9D probabilities were computed by averaging the seven-dimensional (7D) site-specific dissociation probabilities across six impact sites with appropriate relative weights. Our results uncover a distinctive bond-selective effect, demonstrating that the vibrational excitation of a specific bond substantially enhances the cleavage of that excited bond. The product branching ratios are substantially influenced by which bond undergoes excitation, exhibiting a clear preference for the product formed through the cleavage of the excited bond over the alternative product.