The influence of sulfur substitution on the atomic displacement in Bi{sub 2}Ti{sub 2}O{sub 7}

Journal Article · Fri Jan 15 00:00:00 EST 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.11.010· OSTI ID:21372477

Hinojosa, Beverly Brooks; Lang, Paul M ^[1]; Asthagiri, Aravind ^[1]

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1. Department of Chemical Engineering, University of Florida, Gainesville, FL 32611 (United States)

To clarify the role of A{sub 2}O' and B{sub 2}O{sub 6} networks on cation displacement observed in Bi{sub 2}Ti{sub 2}O'O{sub 6}, we used density functional theory calculations to examine the effect of sulfur substitution on the O' and O sites on lone pair formation and resulting atomic displacement observed in Bi{sub 2}Ti{sub 2}O'O{sub 6}. Cation displacement in bismuth titanate is suppressed only when S is substituted on the O' site. Analysis of the electronic structure shows that S substitution on the O' site suppresses the formation of the asymmetric p-type lone pair by modifying the Bi-anion hybridization. Lone pair formation is favored in Bi{sub 2}Ti{sub 2}O'S{sub 6} and the atomic displacement is larger than that observed in Bi{sub 2}Ti{sub 2}O'O{sub 6.} This enhanced displacement is due to weaker Bi-S versus Bi-O interactions leading to significantly stronger hybridization between the Bi and O' states in Bi{sub 2}Ti{sub 2}O'S{sub 6}. We also induced lone pair formation in a metallic bismuth pyrochlore oxide (Bi{sub 2}Ru{sub 2}O'O{sub 6}) by modifying the Bi-O interactions through S substitution on the B{sub 2}O{sub 6} network, indicating atomic displacement on the A{sub 2}O' network may be achieved by modifying the B{sub 2}O{sub 6} network. - Graphical abstract: The electron localization function for Bi{sub 2}Ti{sub 2}O{sub 6}O' and Bi{sub 2}Ti{sub 2}O{sub 6}S' respectively show that sulfur substitution on the O' site will suppress lone pair formation.

• OSTI ID: 21372477
• Journal Information: Journal of Solid State Chemistry, Vol. 183, Issue 1; Other Information: DOI: 10.1016/j.jssc.2009.11.010; PII: S0022-4596(09)00539-8; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANIONS
ATOMIC DISPLACEMENTS
BISMUTH COMPOUNDS
CATIONS
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
OXIDES
PYROCHLORE
RUTHENIUM COMPOUNDS
SULFUR
TITANATES
CALCULATION METHODS
CHALCOGENIDES
CHARGED PARTICLES
ELEMENTS
IONS
MINERALS
NONMETALS
OXYGEN COMPOUNDS
PHYSICAL RADIATION EFFECTS
RADIATION EFFECTS
REFRACTORY METAL COMPOUNDS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
VARIATIONAL METHODS