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Title: New insights into the enigma of boron carbide inverse molecular behavior

Equation of state and compression mechanism of nearly stoichiometric boron carbide B{sub 4}C were investigated using diamond anvil cell single crystal synchrotron X-ray diffraction technique up to a maximum quasi-hydrostatic pressure of 74.0(1) GPa in neon pressure transmitting medium at ambient temperature. No signatures of structural phase transitions were observed on compression. Crystal structure refinements indicate that the icosahedral units are less compressible (13% volume reduction at 60 GPa) than the unit cell volume (18% volume reduction at 60 GPa), contrary to expectations based on the inverse molecular behavior hypothesis, but consistent with spectroscopic evidence and first principles calculations. The high-pressure crystallographic refinements reveal that the nature of the chemical bonds (two, versus three centered character) has marginal effect on the bond compressibility and the compression of the crystal is mainly governed by the force transfer between the rigid icosahedral structural units. - Graphical abstract: Single crystal measurements of equation of state and compression mechanism of B{sub 4}C show that the icosahedral units are less compressibe than the unit cell volume, despite the threei-ceneterd nature of some icosahedral bonds. - Highlights: • Equation of state and compression mechanism of B{sub 4}C were measured to 75 GPa. • No signatures ofmore » structural phase transitions were observed on compression. • Icosahedral units are less compressibe than the unit cell volume. • The nature of the chemical bonds has mariginal effect on the bond compressibility. • The compression is governed by force transfer between the rigid icosahedra.« less
Authors:
 [1] ; ; ;  [1] ;  [2]
  1. Hawaii Institute of Geophysics and Planetology, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, 1680 East West Road, POST Building, Honolulu, HI 96822 (United States)
  2. Center for Advanced Radiation Sources, The University of Chicago, Argonne National Laboratory, 9700 S. Cass Avenue, Building 434, Argonne, IL 60439 (United States)
Publication Date:
OSTI Identifier:
22334265
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 215; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMBIENT TEMPERATURE; BORON CARBIDES; CHEMICAL BONDS; COMPRESSIBILITY; COMPRESSION; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; ELASTICITY; EQUATIONS OF STATE; MONOCRYSTALS; X-RAY DIFFRACTION