Configurational order-disorder induced metal-nonmetal transition in B13C2 studied with first-principles superatom-special quasirandom structure method
2015 (English)In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 92, no 1, 014202Article in journal (Refereed) Published
Due to a large discrepancy between theory and experiment, the electronic character of crystalline boron carbide B13C2 has been a controversial topic in the field of icosahedral boron-rich solids. We demonstrate that this discrepancy is removed when configurational disorder is accurately considered in the theoretical calculations. We find that while the ordered ground state B13C2 is metallic, the configurationally disordered B13C2, modeled with a superatom-special quasirandom structure method, goes through a metal to nonmetal transition as the degree of disorder is increased with increasing temperature. Specifically, one of the chain-end carbon atoms in the CBC chains substitutes a neighboring equatorial boron atom in a B-12 icosahedron bonded to it, giving rise to a B11Ce(BBC) unit. The atomic configuration of the substitutionally disordered B13C2 thus tends to be dominated by a mixture between B-12(CBC) and B11Ce(BBC). Due to splitting of valence states in B11Ce(BBC), the electron deficiency in B-12(CBC) is gradually compensated.
Place, publisher, year, edition, pages
American Physical Society , 2015. Vol. 92, no 1, 014202
IdentifiersURN: urn:nbn:se:liu:diva-120344DOI: 10.1103/PhysRevB.92.014202ISI: 000357484100001OAI: oai:DiVA.org:liu-120344DiVA: diva2:843894
Funding Agencies|Swedish Research Council (VR) [621-2011-4417, 330-2014-6336, 2014-4750]; CeNano at Linkoping University; LiLi-NFM; Swedish Government Strategic Research Area Grant in Materials Science2015-07-312015-07-312016-08-31