A density functional investigation of thiolate-protected bimetal PdAu24(SR)18z clusters: doping the superatom complex

Literature Information

Publication Date 2009-06-11
DOI 10.1039/B904491D
Impact Factor 3.676
Authors

Katarzyna A. Kacprzak, Lauri Lehtovaara, Olga Lopez-Acevedo


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Abstract

Structure, electronic properties, optical absorption and charging properties of methylthiolate-protected bimetal PdAu24(SR)18z (R = Me) clusters with various charge states (−3 ≤z≤ +3) are investigated by using density functional theory. The results are compared to properties of the well-understood singly anionic pure gold complex Au25(SR)18(−1) [J. Akola, M. Walter, H. Häkkinen and H. Grönbeck, J. Am. Chem. Soc., 2008, 130, 3756]. The atomic structure of this all-gold complex can be written in a “divide-and-protect” way [H. Häkkinen, M. Walter and H. Grönbeck, J. Phys. Chem. B, 2006, 110, 9927] as Au13[Au2(SR)3]6(−1) where 6 v-shaped Au2(SR)3 ligands protect the close-to-icosahedral Au13 core and where eight delocalized metal electrons, derived from Au(6s) electrons, comprise a stable closed-shell 1S21P6“superatom” configuration in the core. We show that the di-anion PdAu24(SR)18(−2) is a corresponding eight-electron closed-shell species whereas the clusters PdAu24(SR)18z, −1 ≤z≤ +3, have holes in the 1P HOMO manifold. This indicates that the doping Pd atom remains close to the zero-valent 4d105s0 configuration and does not contribute electrons to the delocalized electron density in the gold core. Structural optimization shows that the all-gold “divide-and-protect” structure motif is robust with respect to replacing the Au by Pd at the center of the core, at the surface of the core or in one of the protecting Au2(SR)3 ligands. However, optical absorption and the HOMO–LUMO and electrochemical gaps depend sensitively on the site of the doping Pd atom, which may turn out be useful for assigning the structure of PdAu24(SR)18 from experimental data.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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