** Reference to paper:

J. Chem. Phys. 156, 214706 (2022)

https://aip.scitation.org/doi/10.1063/5.0094985

** DOI:

10.1063/5.0094985

** Title:

Accurate description of the quantum dynamical surface temperature effects on the dissociative chemisorption of H2 from Cu(111)

** Authors:

B. Smits
L. G. B. Litjens
M. F. Somers

** Contact e-mail:

b.smits@lic.leidenuniv.nl
m.somers@chem.leidenuniv.nl

** Abstract:

Accurately describing surface temperature effects for the dissociative scattering of H2 on a metal surface on a quantum dynamical (QD) level is currently one of the open challenges for theoretical surface scientists.
We present the first QD simulations of hydrogen dissociating on a Cu(111) surface, which accurately describe all relevant surface temperature effects, using the static corrugation model.
The reaction probabilities we obtain show very good agreement with those found using quasi-classical dynamics (QCD), both for individual surface slabs and for an averaged, thus Monte Carlo sampled, set of thermally distorted surface configurations.
Rovibrationally elastic scattering probabilities show a much clearer difference between the QCD and QD results, which appears to be traceable back toward thermally distorted surface configurations with very low dissociation probabilities and underlines the importance of investigating more observables than just dissociation.
By reducing the number of distorted surface atoms included in the dynamical model, we also show that only including one surface atom, or even three surface atoms, is generally not enough to accurately describe the effects of the surface temperature on dissociation and elastic scattering.
These results are a major step forward in accurately describing hydrogen scattering from a thermally excited Cu(111) surface and open up a pathway to better describe reaction and scattering from other relevant crystal facets, such as stepped surfaces, at moderately elevated surface temperatures where quantum effects are expected to play a more important role in the dissociation of H2 on Cu.

** Folder FIG2:

Data files for the constrained, and regular SCM results. Files contain reaction and scattering probabilities, as well as rovib. Quad. alignment parameters where applicable.
Scattering is sorted by final rovibrational state.

** Folder FIG3:

Data files for QD and QCD results.
For QCD, refer to the description of the Figure2 files.

For QD, SCM results reaction is stored in the .reac files per wave-packet. Here the first column is the incidence energy, the second the dissociation probability.
The rovibrationally elastic scattering probabilities are stored in the .vjelas files. Here the first column is again the incidence energy, with all subsequent columns the probability to scatter into the different |n,m| diffraction orders, starting at 0, for (v,J final ) = (v, J initial).
For the EfHP results by Dutta, we refer to their paper and supporting information.

** Folder FIG4:

Data files for QD and QCD results.
QCD and QD are sorted similarly to the Figure 3 folder.
The specific surfaces alpha, beta and gamma are found under Dist0252, Dist0556 and Dist1012.
QCD results for these specific surface slabs are found in their corresponding .dat files, marked as 'QDCompare'.

** Folder FIG5:

Data files for QD and QCD results.
QCD and QD are sorted similarly to the Figure 3 folder.
SCM results using only 1, 3 or 5 surface atoms are marked At1, At3 and At5 respectively, both for QD and QCD.