Probing the Structural Evolution of Gold−Aluminum Bimetallic Clusters (Au₂Al_n⁻, n = 3−11) Using Photoelectron Spectroscopy and Theoretical Calculations

Authors

Navneet S. Khetrapal, University of Nebraska-LincolnFollow
Tian Jian, Brown University
Gary V. Lopez, Brown University
Seema Pande, University of Nebraska - LincolnFollow
Lai-Sheng Wang, Brown UniversityFollow
Xiao Cheng Zeng, University of Nebraska - LincolnFollow

ORCID IDs

Lai-Sheng Wang: 0000-0003-1816-5738

Xiao Cheng Zeng: 0000-0003-4672-8585

Date of this Version

2017

Citation

Published in Journal of Physical Chemistry C 121 (2017), pp 18234−18243.

DOI: 10.1021/acs.jpcc.7b04997

Comments

Copyright © 2017 American Chemical Society. Used by permission.

Abstract

We report a combined photoelectron spectroscopy and theoretical study of the structural evolution of aluminum cluster anions doped with two gold atoms, Au₂Al_n^– (n = 3−11). Well-resolved photoelectron spectra have been obtained at several photon energies and are used to compare with theoretical calculations to elucidate the structures of the bimetallic clusters. Global minima of the Au₂Al_n^– clusters were searched using the basin-hopping method combined with density functional theory calculations. Vertical detachment energies were computed for the low-lying isomers with the inclusion of spin−orbit effects and were used to generate simulated photoelectron spectra. Au₂Al₂^– was previously found to exhibit a tetrahedral structure, whereas Au₂Al₃^– is found currently to be planar. Beyond n = 3, the global minima of Au₂Al_n^– are dominated by three-dimensional structures. A robust square-bipyramidal Al₆ motif is observed for n = 6−9, leading to a highly stable tubular-like global minimum for Au₂Al₉^–. Compact three-dimensional structures are observed for n = 10 and 11. Except for Au₂Al₄^–, Au₂Al₆^–, and Au₂Al₇^–, the two gold atoms are separated in these digold-atom-doped aluminum clusters due to the strong Au−Al interactions.