posted on 2024-02-28, 18:40authored byNick Gerrits, Bret Jackson, Annemie Bogaerts
Molecular dynamics simulations are essential for a better
understanding
of dissociative chemisorption on metal surfaces, which is often the
rate-controlling step in heterogeneous and plasma catalysis. The workhorse
quasi-classical trajectory approach ubiquitous in molecular dynamics
is able to accurately predict reactivity only for high translational
and low vibrational energies. In contrast, catalytically relevant
conditions generally involve low translational and elevated vibrational
energies. Existing quantum dynamics approaches are intractable or
approximate as a result of the large number of degrees of freedom
present in molecule–metal surface reactions. Here, we extend
a ring polymer molecular dynamics approach to fully include, for the
first time, the degrees of freedom of a moving metal surface. With
this approach, experimental sticking probabilities for the dissociative
chemisorption of methane on Pt(111) are reproduced for a large range
of translational and vibrational energies by including nuclear quantum
effects and employing full-dimensional simulations.