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Title: Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand asmore » suitable candidates with enhanced superhalogens properties.« less
Authors:
; ; ; ;  [1] ;  [2]
  1. MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)
  2. Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)
Publication Date:
OSTI Identifier:
22493908
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Advances; Journal Volume: 5; Journal Issue: 6; Other Information: (c) 2015 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; ATOMS; BERYLLIUM COMPOUNDS; CALCIUM COMPOUNDS; CARBON NITRIDES; CHLORINE; COMPARATIVE EVALUATIONS; CYANIDES; ELECTRON DETACHMENT; ELECTRONS; EV RANGE; FLUORINE; KINETIC ENERGY; LIGANDS; MOLECULAR CLUSTERS; POTENTIALS; STABILITY; VALENCE