Issue 13, 2021

Designing new SRP density functionals including non-local vdW-DF2 correlation for H2 + Cu(111) and their transferability to H2 + Ag(111), Au(111) and Pt(111)

Abstract

Specific reaction parameter density functionals (SRP-DFs) that can describe dissociative chemisorption molecular beam experiments of hydrogen (H2) on cold transition metal surfaces with chemical accuracy have so far been shown to be only transferable among different facets of the same metal, but not among different metals. We design new SRP-DFs that include non-local vdW-DF2 correlation for the H2 + Cu(111) system, and evaluate their transferability to the highly activated H2 + Ag(111) and H2 + Au(111) systems and the non-activated H2 + Pt(111) system. We design our functionals for the H2 + Cu(111) system since it is the best studied system both theoretically and experimentally. Here we demonstrate that a SRP-DF fitted to reproduce molecular beam sticking experiments for H2 + Cu(111) with chemical accuracy can also describe such experiments for H2 + Pt(111) with chemical accuracy, and vice versa. Chemically accurate functionals have been obtained that perform very well with respect to reported van der Waals well geometries, and which improve the description of the metal over current generalized gradient approximation (GGA) based SRP-DFs. From a systematic comparison of our new SRP-DFs that include non-local correlation to previously developed SRP-DFs, for both activated and non-activated systems, we identify non-local correlation as a key ingredient in the construction of transferable SRP-DFs for H2 interacting with transition metals. Our results are in excellent agreement with experiment when accurately measured observables are available. It is however clear from our analysis that, except for the H2 + Cu(111) system, there is a need for more, more varied, and more accurately described experiments in order to further improve the design of SRP-DFs. Additionally, we confirm that, when including non-local correlation, the sticking of H2 on Cu(111) is still well described quasi-classically.

Graphical abstract: Designing new SRP density functionals including non-local vdW-DF2 correlation for H2 + Cu(111) and their transferability to H2 + Ag(111), Au(111) and Pt(111)

Supplementary files

Article information

Article type
Paper
Submitted
01 out 2020
Accepted
19 nov 2020
First published
19 nov 2020
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2021,23, 7875-7901

Designing new SRP density functionals including non-local vdW-DF2 correlation for H2 + Cu(111) and their transferability to H2 + Ag(111), Au(111) and Pt(111)

E. W. F. Smeets and G. Kroes, Phys. Chem. Chem. Phys., 2021, 23, 7875 DOI: 10.1039/D0CP05173J

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