Journal article

Authors list: Mollenhauer, D; Gaston, N

Publication year: 2014

Pages: 986-997

Journal: Journal of Computational Chemistry

Volume number: 35

Issue number: 13

DOI Link: https://doi.org/10.1002/jcc.23578

Publisher: Wiley

Abstract: 

Ligand‐protected metal clusters are difficult to describe within density
functional theory due to the need to treat the electronic structure of
the cluster, possible charge transfer between the ligands and the
cluster, and weak ligand–ligand interactions in a balanced manner. We
demonstrate the use of an appropriate, stepwise benchmarking process
that accounts for the nonadditivity of these different contributions to
stability and catalytic activity. We consider both open‐ and
closed‐shell clusters, differently charged systems, and ligands of
increasing complexity for gold phosphine systems. The use of a
dispersion correction to density functional calculations was found to be
crucial for both structure optimization and the calculation of binding
energies. We find that PBE‐D3 performs well with a variation in
energetics of 0.7–10.9 kcal/mol, PBE0‐D3 better with 0.0–3.3 kcal/mol,
and B2PLYP‐D3 the best with 0.2–2.4 kcal/mol, when compared to the best
available benchmark [CCSD(T) or SCS‐MP2]. Our systematic procedure
clarifies that these functionals all give accurate results for certain
cases, but for the total performance over a range of interactions, they
perform in accordance with Jacob's ladder.

Harvard Citation style: Mollenhauer, D. and Gaston, N. (2014) A balanced procedure for the treatment of cluster–ligand interactions on gold phosphine systems in catalysis, Journal of Computational Chemistry, 35(13), pp. 986-997. https://doi.org/10.1002/jcc.23578

APA Citation style: Mollenhauer, D., & Gaston, N. (2014). A balanced procedure for the treatment of cluster–ligand interactions on gold phosphine systems in catalysis. Journal of Computational Chemistry. 35(13), 986-997. https://doi.org/10.1002/jcc.23578