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High Spin Ground States in Matryoshka Actinide Nanoclusters: A Computational Study
Author(s) -
Hu HanShi,
Kaltsoyannis Nikolas
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705196
Subject(s) - nanoclusters , actinide , cluster (spacecraft) , ground state , spin (aerodynamics) , spin states , chemistry , crystallography , atomic physics , physics , materials science , nanotechnology , inorganic chemistry , thermodynamics , computer science , programming language
Abstract Inspired by the experimentally synthesized Na 12 @[(UO 2 )(O 2 ) 1.5 ] 20 8− (“Na 12 @U 20 ”) cluster, we have explored computationally the substitution of the Na cations by many other metals. 6 other M 12 @U 20 systems are found to be stable ( M =K + , Rb + , Cs + , Ag + , Mg 2+ , Fe 2+ ). For 3 of these (Mg 2+ , Ag + and Na + ), the cluster can support a group 16 dianion at its center, forming a new type of Matryoshka (“Russian Doll”) actinide nanocluster E @ M 12 @U 20 (E=S 2− , Se 2− , Te 2− , and Po 2− ). These systems have 3‐shell, onion‐like geometries with nearly perfect I h symmetry. Seeking to create clusters with very high spin ground states, we have replaced M by Mn 2+ and U 20 by Np 20 and Pu 20 , generating clusters with maximum possible S values of 80/2 and 100/2 respectively. Only in the presence of a central S 2− , however, are these electronic configurations the most stable; the novel Matryoshka Pu nanocluster S@Mn 12 @Pu 20 is predicted to have the highest ground state spin yet reported for a molecular cluster.