2009/09/30 by Dan J. Harding, D. J. Harding, T. R. Walsh +15 · 58 citations
Chemistry · Engineering · Materials Science · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical physics #Chemistry #Cluster (spacecraft) #Computational chemistry #Computer science #Crystal structure #Crystallography #Density functional theory #Dissociation (chemistry) #Gas phase #Hybrid functional #Materials science #Molecular Junctions and Nanostructures #Molecular physics #Nanocluster Synthesis and Applications #Octahedron #Physical chemistry #Physics #Quantum mechanics #Spectroscopy #physics.atm-clus
paper · pdf · doi:10.1063/1.3285266
published in The Journal of Chemical Physics 132(1), 011101 (American Institute of Physics) · 10 pages, 3 figures
arxiv created 2009/09/30 · openalex publication_date 2010/01/06 · arxiv updated 2015/05/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
The geometric structure of the Rh(8) (+) cation is investigated using a combination of far-infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. The energetic ordering of the different structural motifs is found to depend sensitively on the choice of pure or hybrid exchange functionals. Comparison of experimental and calculated spectra suggests the cluster to have a close-packed, bicapped octahedral structure, in contrast to recent predictions of a cubic structure for the neutral cluster. Our findings demonstrate the importance of including some exact exchange contributions in the DFT calculations, via hybrid functionals, when applied to rhodium clusters, and cast doubt on the application of pure functionals for late transition metal clusters in general.