DOI: 10.4121/aa293545-0c96-41c5-8bcf-cdf1374b3571.v1
title: Supporting data: Reaction barriers at metal surfaces computed using the random phase approximation: Can we beat DFT in the generalized gradient approximation?

description: Objective: Compute barrier heights for dissociative chemisorption of H2 on Al(110) and Cu(111) using- the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem,- hybrid functionals and- density functional theory in the generalized gradient approximation.Method: Electronic structure calculations.Notes: The data provided here is the raw data required to reproduce results presented in publication sited under "Linked sources"<br>The data collection in the two databases (database_H2onCu_flat.db and database_H2onAl_flat.db) provides computed energies for dissociative chemisorption barriers and asymptotic geometries relevant to the dissociative chemisorption reaction of H2 on Al(110) and Cu(111). The energies were computed using density functional theory approaches (DFT) (including hybrid functionals) and the the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem (ACFDT-RPA). All energies were obtained using the code VASP6. Energies have been obtained for various different parameters, including different functionals, different sampling of the Brillouin zone (k-points), different plane wave cutoffs (Ecut), different smearing parameters, different slab thicknesses, different vacuum thicknesses ect as specified in the databases. Taken together, the data can be used to determine well converged barrier heights for the given barrier geometry for different DFT functionals and ACFDT-RPA as described in the relevant publication (see "Linked sources") and analysis.tar.gz. The resulting barriers are summarized in barriers_summary.txt, together with additional values from literature (see file for references) and experimentally motivated references derived in the linked publication based on results from Refs. [1,2,3,4]. The barrier geometries are taken from Refs. [1,2].Additionally, the data collection contains densities of states as computed with PBE and GW at the transition state geometry for H2 dissociating on Al(110) and Cu(111) as computed with VASP and a density of states projected onto molecular orbitals computed in GPAW. These data are relevant to judge the influence of possible band misalignments in the DFT calculations.For all data presented, the data collection provides the required information to redo the calculations. See README for further information.Please contact the authors to obtain scripts used to produce the final plots in the linked publication.<br>[1] Powell, A. D.; Kroes, G.-J.; Doblhoff-Dier, K. Quantum Monte Carlo Calculations on Dissociative Chemisorption of H2 + Al(110): Minimum Barrier Heights and Their Comparison to DFT Values. <em>J. Chem. Phys.</em> <strong>2020</strong>, <em>153</em> (22), 224701. https://doi.org/10.1063/5.0022919.[2] Doblhoff-Dier, K.; Meyer, J.; Hoggan, P. E.; Kroes, G.-J. Quantum Monte Carlo Calculations on a Benchmark Molecule–Metal Surface Reaction: H<sub>2</sub> + Cu(111). <em>J. Chem. Theory Comput.</em> <strong>2017</strong>, <em>13</em> (7), 3208–3219. https://doi.org/10.1021/acs.jctc.7b00344.[3] Diaz et al, Science 326, 5954, 832 (2009), https://doi.org/10.1126/science.1178722[4] Powell et al, J. Phys. Chem. Lett. 2024, 15, 1, 307–315 (2024), https://doi.org/10.1021/acs.jpclett.3c02972<br>