Published Research - Department of Chemistry


Date of this Version



Published in Journal of Physical Chemistry C 122 (2018), pp 6947−6954.

doi 10.1021/acs.jpcc.8b00166


Copyright © 2018 American Chemical Society. Used by permission.


The structures of gold-doped bismuth clusters, AuBin (n = 4−8), are investigated through a joint photoelectron spectroscopy and density functional theory (DFT) study. Well-resolved photoelectron spectra are obtained at several photon energies. Global minimum searches coupled with DFT calculations yield low-lying structures, whose relative energies are further evaluated by single-point energy calculations at the CCSD(T) level of theory. Vertical detachment energies are calculated with the inclusion of spin−orbit effects to compare with the experimental data. Three-dimensional structures are found to be dominant in this size range, while a planar low-lying isomer is observed only for AuBi4. The AuBi6 cluster possesses a “bow-tie-like” global minimum structure. Major isomers of the other clusters studied here can all be viewed to possess this structural motif. The gold dopant favors increasingly higher coordination with bismuth in AuBin (n = 4−8). Chemical bonding analyses are performed to understand the geometric and electronic structure evolution of these bimetallic clusters. The gold atom interacts with neighboring bismuth atoms via localized σ bonds at low-coordination sites but via delocalized σ bonds at high-coordination sites. Greater charge transfer from Bi to Au is found for higher-coordinated Au. Molecular dynamics simulations indicate that the assigned global minimum of AuBi7 is a highly stable structure, whereas the minor isomer of AuBi7 displays a fluxional behavior.

Pande JPC 2018 Structural Evolution SUPPL 1.pdf (2064 kB)
Energy tables, simulated and experimental photoelectron spectra for all the top candidate isomers of AuBin− (n = 4−8), and rmsd of simulated spectra of the major isomers

Pande JPC 2018 Structural Evolution MOVIE 1.mpg (8792 kB)
Fairly stable isomer I of AuBi7− with its intact structure during the simulation

Pande JPC 2018 Structural Evolution MOVIE 2.mpg (8800 kB)
Relatively unstable isomer II of AuBi7− undergoing structural transformations to isomers that appear like isomers III and IV