Exploring Structural Diversity and Fluxionality of Pt _n ( n = 10–13) Clusters from First-Principles

Journal Article · Wed Jan 04 04:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b11968· OSTI ID:1480448

Fung, Victor ^[1]; Jiang, De-en ^[1]

---

1. Department of Chemistry, University of California, Riverside, California 92521, United States

Subnanometer transition-metal clusters have been shown to possess catalytic activity that is size-dependent. It has been suggested that the fluxionality of these small clusters may be closely related to their catalytic activity. Here we use basin-hopping global optimization with density functional theory (DFT) to study the energy landscape of Ptn (n = 10–13) clusters. We analyze a large set of local minima obtained from the DFT-based global optimization. We find that Pt10 is unique with respect to the other studied sizes in its structural landscape, which shows a single, distinct structural motif corresponding to a tetrahedral global minimum. In contrast, Pt11–13 all display characteristics of high fluxionality with the presence of multiple significantly differing structural features in the low-energy region, as characterized by coordination number, interatomic distances, and shape. These observations demonstrate the structural diversity and fluxionality of the subnanometer Pt clusters that will have important implications for catalysis.

• Research Organization: Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
• DOE Contract Number: AC02-05CH11231
• OSTI ID: 1480448
• Journal Information: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 20 Vol. 121; ISSN 1932-7447
• Country of Publication: United States
• Language: English