SmB6-Cluster Anion: Covalency Involving f Orbitals.
While boride clusters of alkali and transition metals have been observed and extensively characterized, so far little is known about lanthanide-boron clusters. Lanthanide-boride solids are intriguing, however, and therefore it is of interest to understand the fundamental electronic properties of such systems, also on the subnano scale. We report a joint experimental photoelectron spectroscopic and theoretical study of the SmB6-anion, iso-stoichiometric to the SmB6solid-a topological Kondo insulator. The cluster is found to feature strong static and dynamic electron correlations and relativistic components, calling for treatment with CASPT2 and up sixth-order Douglass-Kroll-Hess (DKH) relativistic correction. The cluster has a C2vstructure and covalent Sm-B bonds facilitated by f atomic orbitals on Sm, which are typically thought to be contracted and inert. Additionally, the cluster retains the double antiaromaticity of the B62-cluster.
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095, United States.
Paul J
PJ
Robinson
Department of Chemistry and Materials Science, Johns Hopkins University , 3400 N. Charles Street, Baltimore, Maryland 21218, United States.
Xinxing
X
Zhang
Department of Chemistry and Materials Science, Johns Hopkins University , 3400 N. Charles Street, Baltimore, Maryland 21218, United States.
Tyrel
T
McQueen
Department of Chemistry and Materials Science, Johns Hopkins University , 3400 N. Charles Street, Baltimore, Maryland 21218, United States.
Kit H
KH
Bowen
Department of Chemistry and Biochemistry, University of California, Los Angeles , 607 Charles E. Young Drive East, Los Angeles, California 90095, United States.|California NanoSystems Institute, 570 Westwood Plaza, Building 114, Los Angeles, California 90095, United States.
Anastassia N
http://orcid.org/0000-0002-3003-1911
AN
Alexandrova