Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

doi:10.1063/1.4867009

	Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands
	Yin, Bing 1,2; Li, Teng 1; Li, Jin-Feng 1; Yu, Yang 1; Li, Jian-Li 1; Wen, Zhen-Yi 1,2; Jiang, Zhen-Yi 2
刊名	JOURNAL OF CHEMICAL PHYSICS
	2014-03-07
卷号	140
ISSN号	0021-9606
DOI	10.1063/1.4867009
文献子类	Article
英文摘要	The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg-2(CN)(5)](-) clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower 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 detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties. (C) 2014 AIP Publishing LLC.
WOS关键词	ELECTRON-BINDING ENERGIES ; ZETA VALENCE QUALITY ; GAUSSIAN-BASIS SETS ; PHOTOELECTRON-SPECTROSCOPY ; STABILITY ; LI ; BR ; AFFINITIES ; COMPLEXES ; CLUSTERS
语种	英语
出版者	AMER INST PHYSICS
WOS记录号	WOS:000334067400013
内容类型	期刊论文
源URL	[http://119.78.100.186/handle/113462/49307]
专题	中国科学院近代物理研究所
通讯作者	Yin, Bing
作者单位	1.NW Univ Xian, MOE Key Lab Synthet & Nat Funct Mol Chem, Shaanxi Key Lab Phys Inorgan Chem, Coll Chem & Mat Sci, Xian 710069, Peoples R China 2.NW Univ Xian, Inst Modern Phys, Xian 710069, Peoples R China
推荐引用方式 GB/T 7714	Yin, Bing,Li, Teng,Li, Jin-Feng,et al. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands[J]. JOURNAL OF CHEMICAL PHYSICS,2014,140.
APA	Yin, Bing.,Li, Teng.,Li, Jin-Feng.,Yu, Yang.,Li, Jian-Li.,...&Jiang, Zhen-Yi.(2014).Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands.JOURNAL OF CHEMICAL PHYSICS,140.
MLA	Yin, Bing,et al."Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands".JOURNAL OF CHEMICAL PHYSICS 140(2014).