** Reference to paper:
J. Phys. Chem. C 2024, 128, 45, 19182-19196

** DOI:
10.1021/acs.jpcc.4c05466

Weblink:
https://doi.org/10.1021/acs.jpcc.4c05466

** Title:
O 2 Dissociation on Cu(111) Dynamics on a Novel Screened Hybrid Van-der-Waals DFT Potential Energy Surface

** Authors:
van Bree, Robert
Kroes, Geert-Jan

** Contact e-mail:
r.a.b.van.bree@lic.leidenuniv.nl
g.j.kroes@chem.leidenuniv.nl

** Abstract:
The dissociative chemisorption (DC) of O 2 on Cu(111) has been extensively studied by both theory and
experiment. Different experiments disagree on the underlying mechanisms (direct or indirect) for the
sticking of O 2 . Thus far, studies based on density functional theory (DFT) favour the indirect mechanism.
However, DFT has not fully resolved the discussion as DFT based on the generalised gradient
approximation (GGA) has always substantially overestimated the reactivity and sticking probabilities of
O 2 on Cu(111) and other Cu surfaces. Recent work indicated that this overestimation is due to the
failure of GGA DFT to describe molecule-metal systems where the charge transfer energy ( E CT ), i.e., the
work function of the metal surface minus the electron affinity of the molecule, is below 7 eV . O 2 +
Cu(111) is one such system. This work presents computed sticking probabilities for O 2 + Cu(111) based
on the HSE06-1/2x-VdWDF2 screened hybrid Van der Waals density functional (DF), which is applied
self-consistently. A six-dimensional static surface potential energy surface (PES) was constructed using
the corrugation reducing procedure. This PES was used to perform quasi-classical trajectory
calculations to compute the sticking probabilities of O 2 + Cu(111). For the first time, we present DFT-
based sticking probabilities that underestimate the experimental sticking probabilities. While
reproducing the experimental results would have been even more desirable the fact that we found a
DF which underestimates the measured sticking probabilities means a DF using a lower fraction of exact
exchange will most likely describe the O 2 + Cu(111) system with high accuracy. Furthermore, our work
shows evidence for the presence of both indirect and direct dissociative chemisorption. The indirect
precursor-mediated mechanism occurs for low incidence energy O 2 . The mechanism is supplanted by
a direct dissociative mechanism at higher incidence energies. Lastly, our work suggests that the Cu
surface temperature may also effect the dissociation mechanism, but this still needs further verification
with a different theoretical framework that allows for the simulation of surface temperature.


** Description of files:
CRP_Data.tar.gz				Tarbal that contains all the Data for the CRP PES
DFT-3DPES-InputFiles			Dir of DFT input files for the atomic (3D) PES data generation
DFT-6DPES-InputFiles			Dir of DFT input files for all the molecule (6D) PES data generation
HSE06-12x-VdWDF2-LatticeConstant	Dir containing the lattice relaxation details
QCT_Input-Results.tar.gz  		Tarbal of all the QCT dynamics input and result files
Slab_Info.txt				Text file containing all the information about the slab relaxation and data