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Title: First principles study of electronic structure for cubane-like and ring-shaped structures of M{sub 4}O{sub 4}, M{sub 4}S{sub 4} clusters (M = Mn, Fe, Co, Ni, Cu)

Spin-polarized DFT has been used to perform a comparative study of the geometric structures and electronic properties for isolated M{sub 4}X{sub 4} nano clusters between their two stable isomers - a planar rhombus-like 2D structure and a cubane-like 3D structure with M = Mn, Fe, Co, Ni, Cu ; X = O, S. These two structural patterns of the M{sub 4}X{sub 4} clusters are commonly found as building blocks in several poly-nuclear transition metal complexes in inorganic chemistry. The effects of the van der Waals corrections to the physical properties have been considered in the electronic structure calculations employing the empirical Grimme’s correction (DFT+D2). We report here an interesting trend in their relative structural stability - the isolated M{sub 4}O{sub 4} clusters prefer to stabilize more in the planar structure, while the cubane-like 3D structure is more favorable for most of the isolated M{sub 4}S{sub 4} clusters than their planar 2D counterparts. Our study reveals that this contrasting trend in the relative structural stability is expected to be driven by an interesting interplay between the s-d and p-d hybridization effects of the constituents’ valence electrons.
Authors:
 [1] ;  [2]
  1. Department of Condensed Matter Physics and Material Sciences, S.N. Bose National Centre for Basic Sciences, JD Block, Sector-III, Salt Lake City, Kolkata 700 098 (India)
  2. Department of Physics, Aliah University, IIA/27- Newtown, Kolkata 700 156 (India)
Publication Date:
OSTI Identifier:
22492206
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Advances; Journal Volume: 5; Journal Issue: 11; Other Information: (c) 2015 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; COBALT OXIDES; COPPER OXIDES; CORRECTIONS; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; ELECTRONS; IRON SULFIDES; ISOMERS; MANGANESE OXIDES; NICKEL SULFIDES; SOLID CLUSTERS; SPIN ORIENTATION; VALENCE; VAN DER WAALS FORCES