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Chemical bonding topology of superconductors:I. Ternary molybdenum chalcogenides (Chevrel phases)

Authors
Journal
Journal of Solid State Chemistry
0022-4596
Publisher
Elsevier
Publication Date
Volume
71
Issue
1
Identifiers
DOI: 10.1016/0022-4596(87)90162-9
Disciplines
  • Chemistry
  • Mathematics
  • Physics

Abstract

Abstract Models for the chemical bonding topologies of ternary molybdenum chalcogenides (Chevrel phases) are derived using methods based on graph theory. The MMo 6S 8 Chevrel phases as well as their selenium analogs are viewed as three-dimensional lattices of edge-localized discrete Mo 6 octahedra linked electronically through interoctahedral metal-metal interactions. This porously delocalized chemical bonding topology is suggested to be a feature of superconducting systems exhibiting relatively high critical temperatures and magnetic fields. Fusion of molybdenum octahedra through face-sharing leads successively to the Mo 9S 11 naphthalene analog and the Mo 12S 14 anthracene analog, with increasing fusion leading to increasing delocalization of the chemical bonding topology within individual molybdenum cluster units. The infinite limit of such fusion of molybdenum octahedra corresponds to the infinite chain pseudo-one-dimensional metals [ M 2Mo 6 X 6] ∞ ( M = monovalent metal; X = S, Se, Te) which are formulated with globally delocalized octahedral cavities. Thus the progression from discrete Mo 6 octahedra in the MMo 6S 8 Chevrel phases to the infinite chains of face-fused octahedra in [ M 2Mo 6 X 6] ∞ leads to a progression from an edge-localized to a globally delocalized chemical bonding topology.

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