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Title: Could the description on polynuclear superhalogens by DFT be comparable with high-level ab initio results? A comparison between DFT and CCSD(T)

A systematic density functional theory study including 17 exchange-correlation functionals was performed on different types of superhalogens with high level coupled-cluster single double including perturbative triple excitations (CCSD(T)) results as the reference. The superhalogens selected here cover the ranges from mononuclear to polynuclear structures and from structures with halogen-atom ligands to those with non-halogen ligands, e.g., [MgX{sub 3}]{sup −}, [Mg{sub 2}X{sub 5}]{sup −}, and [Mg{sub 3}X{sub 7}]{sup −} (X = F, Cl, CN). It is clearly indicated that three double-hybrid functionals B2T-PLYP, B2GP-PLYP, B2K-PLYP as well as the range-separated hybrid functional ωB97X are capable of providing results which approach the accuracy at the CCSD(T) level. The basis set effect is usually moderate and, in most cases, it is enough to utilize the basis set of triple-ξ quality, e.g., Def2-TZVP. In addition, the results of the HF and MP2 method are also acceptable here, especially for polynuclear superhalogens where CCSD(T) is probably unpractical.
Authors:
; ; ; ; ;  [1]
  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)
Publication Date:
OSTI Identifier:
22493717
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 5; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ATOMS; CARBON NITRIDES; COMPARATIVE EVALUATIONS; CYANIDES; DENSITY FUNCTIONAL METHOD; EXCITATION; HALOGENS; HYBRIDIZATION; HYDROFLUORIC ACID; LIGANDS