liu.seSearch for publications in DiVA
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
A Density Functional Benchmark for Dehydrogenation and Dehalogenation Reactions on Coinage Metal Surfaces
Linköping University, Department of Physics, Chemistry and Biology, Materials design. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-7905-9587
Linköping University, Department of Physics, Chemistry and Biology, Materials design. Linköping University, Faculty of Science & Engineering.
Linköping University, Department of Physics, Chemistry and Biology, Materials design. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-1345-0006
2025 (English)In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 26, no 1, article id e202400865Article in journal (Refereed) Published
Abstract [en]

The on-surface synthesis of low-dimensional organic nanostructures has been extensively investigated through both experimental and theoretical methods, particularly by density functional theory (DFT). However, the complex mixture of interactions often poses challenges within the DFT framework, and there is a knowledge-gap regarding how the choice of DFT approach affects the computed results. Here, five different approaches including vdW interactions, i. e., PBE+D3, PBE+vdW(surf), rev-vdWDF2, r(2)SCAN+rVV10 and BEEF-vdW, are employed to describe three prototypical on-surface reactions; dehydrogenation of benzene, debromination of bromobenzene, and deiodination of iodobenzene on the (111) facets of the coinage metals. Overall, rev-vdW-DF2 outperforms the other methods in describing benzene adsorption, whereas BEEF-vdW falls short. For dehydrogenation and debromination on Cu(111), all functionals except BEEF-vdW give reasonable activation energies compared to experiments. A similar trend is observed for Ag(111) and Au(111), with BEEF-vdW yielding significantly higher activation and reaction energies. For dehalogenation, all the five vdW approaches correctly capture the reactivity trend - Cu(111)>Ag(111)>Au(111) - and the expected hierarchy between bromobenzene desorption and carbon-bromine activation. Only BEEF-vdW fails to predict the faster kinetics of deiodination than the iodobenzene desorption. Our work forms a basis for evaluating density functionals in describing chemical reactions on surfaces.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH , 2025. Vol. 26, no 1, article id e202400865
Keywords [en]
vdWs interactions; DFT; On-surface synthesis; Dehydrogenation; Dehalogenation
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-210165DOI: 10.1002/cphc.202400865ISI: 001358127700001PubMedID: 39353856Scopus ID: 2-s2.0-85208980132OAI: oai:DiVA.org:liu-210165DiVA, id: diva2:1917637
Note

Funding Agencies|Gran Gustafsson Foundation for Research in Natural Sciences and Medicine; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; Swedish Research Council [2022-06725]

Available from: 2024-12-03 Created: 2024-12-03 Last updated: 2025-09-18

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMedScopus

Search in DiVA

By author/editor
Chen, LinRosén, JohannaBjörk, Jonas
By organisation
Materials designFaculty of Science & Engineering
In the same journal
ChemPhysChem
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 85 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf