Journal article

Authors list: Mollenhauer, D; Gaston, N

Publication year: 2016

Pages: 29686-29697

Journal: Physical Chemistry Chemical Physics

Volume number: 18

Issue number: 43

DOI Link: https://doi.org/10.1039/C6CP04562F

Publisher: Royal Society of Chemistry

Abstract: 

A systematic evaluation of small phosphine ligand-protected gold
clusters with six to nine gold atoms using density functional theory
with dispersion correction has been performed in order to understand the
major factors determining stability, including its size, shape, and
charge dependence. We show that the charge per atom of the cluster is
much more important for the interaction between the ligand shell and
gold cluster than the system size. Thus, strong charge transfer effects
determine the binding strength between the ligand shell and cluster. The
clusters in this series are all non-spherical and exhibit large
HOMO–LUMO gaps (above 2.7 eV). Analysis of the delocalized nature of the
electronic states at the centre of the clusters demonstrates the
presence of nascent superatomic states. However the number of
delocalized electrons in these systems is significantly influenced by
the charge transfer from the phosphine ligands, contrary to the usual
accounting rule for superatom complex systems. Thus, not only electron
withdrawing but also charge transfer effects should be considered to
influence the superatomic structure of charged ligand surrounded
clusters. In consequence in the phosphine gold cluster series under
consideration the systems Au₇(PPh₃)₇⁺ and Au₈(PPh₃)₈²⁺
exhibit nearly fully filled S and P states and the HOMO–LUMO gap
increases by 0.2 eV and 0.9 eV, respectively. The interpretation for the
stability of the gold phosphine systems is in agreement with
experimental results and demonstrates the importance of the superatomic
concept.

Harvard Citation style: Mollenhauer, D. and Gaston, N. (2016) Phosphine passivated gold clusters: how charge transfer affects electronic structure and stability, Physical Chemistry Chemical Physics, 18(43), pp. 29686-29697. https://doi.org/10.1039/C6CP04562F

APA Citation style: Mollenhauer, D., & Gaston, N. (2016). Phosphine passivated gold clusters: how charge transfer affects electronic structure and stability. Physical Chemistry Chemical Physics. 18(43), 29686-29697. https://doi.org/10.1039/C6CP04562F