Published in

American Physical Society, Physical review B, 12(86), 2012

DOI: 10.1103/physrevb.86.125430

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Hybrid density functional study of small Rhn(n=2−15)clusters

Journal article published in 2012 by Juarez L. F. Da Silva, Maurício J. Piotrowski ORCID, F. Aguilera-Granja
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

The physical properties of small rhodium clusters, Rhn, have been in debate due to the shortcomings of density functional theory (DFT). To help in the solution of those problems, we obtained a set of putative lowest energy structures for small Rhn (n= 2–15) clusters employing hybrid-DFT and the generalized gradient approximation (GGA). For n= 2–6, both hybrid and GGA functionals yield similar ground-state structures (compact), however, hybrid favors compact structures for n=7–15, while GGA favors open structures based on simple cubic motifs. Thus, experimental results are crucial to indicate the correct ground-state structures, however, we found that a unique set of structures (compact or open) is unable to explain all available experimental data. For example, the GGA structures (open) yield total magnetic moments in excellent agreement with experimental data, while hybrid structures (compact) have larger magnetic moments compared with experiments due to the increased localization of the 4d states. Thus, we would conclude that GGA provides a better description of the Rhn clusters, however, a recent experimental-theoretical study [ Harding et al. J. Chem. Phys. 133 214304 (2010)] found that only compact structures are able to explain experimental vibrational data, while open structures cannot. Therefore, it indicates that the study of Rhn clusters is a challenging problem and further experimental studies are required to help in the solution of this conundrum, as well as a better description of the exchange and correlation effects on the Rhn clusters using theoretical methods such as the quantum Monte Carlo method.