Journal article

Authors list: Luy, JN; Henkel, P; Grigjanis, D; Jung, J; Mollenhauer, D; Tonner-Zech, R

Publication year: 2022

Pages: 179-189

Journal: Journal of Computational Chemistry

Volume number: 44

Issue number: 3

ISSN: 0192-8651

Open access status: Hybrid

DOI Link: https://doi.org/10.1002/jcc.26855

Publisher: Wiley

Abstract: 
On-surface synthesis has become a thriving topic in surface science. The Ullmann coupling reaction is the most applied synthetic route today, but the nature of the organometallic intermediate is still under discussion. We investigate the bonding nature of prototypical intermediate species (phenyl, naphthyl, anthracenyl, phenanthryl, and triphenylenyl) on the Cu(111) surface with a combination of plane wave and atomic orbital basis set methods using density functional theory calculations with periodic boundary conditions. The surface bonding is shown to be of covalent nature with a polarized shared-electron bond supported by pi-back donation effects using energy decomposition analysis for extended systems (pEDA). The bond angle of the intermediates is determined by balancing dispersion attraction and Pauli repulsion between adsorbate and surface. The latter can be significantly reduced by adatoms on the surface. We furthermore investigate how to choose computational parameters for pEDA of organic adsorbates on metal surfaces efficiently and show that bonding interpretation requires consistent choice of the density functional.

Harvard Citation style: Luy, J., Henkel, P., Grigjanis, D., Jung, J., Mollenhauer, D. and Tonner-Zech, R. (2022) Bonding character of intermediates in on-surface Ullmann reactions revealed with energy decomposition analysis, Journal of Computational Chemistry, 44(3), pp. 179-189. https://doi.org/10.1002/jcc.26855

APA Citation style: Luy, J., Henkel, P., Grigjanis, D., Jung, J., Mollenhauer, D., & Tonner-Zech, R. (2022). Bonding character of intermediates in on-surface Ullmann reactions revealed with energy decomposition analysis. Journal of Computational Chemistry. 44(3), 179-189. https://doi.org/10.1002/jcc.26855