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Electronic structure effects in the vectorial bond-valence model
-
Barry R. Bickmore
,
Matthew F.C. Wander
Published/Copyright:
March 7, 2015
Abstract
The vectorial bond-valence model (VBVM) describes the spatial distribution of bonds to each atom in a system in terms of the vector sum of the incident bond valences. It has been applied in the past to cations not subject to electronic structure effects (e.g., lone-pair or Jahn-Teller effects) in which case the expectation is that the vector sum will be approximately zero. Here we analyze 178 simpleoxide crystal structures and show that the vectorial bond-valence sum is a predictable function of the atomic valence (oxidation state) of each atom and the valence of the strongest bond to atoms for which second-order Jahn-Teller and lone-pair effects play a role in determining molecular geometry. Outliers are uniformly metastable or unstable under ambient conditions, suggesting that deviation from ideal vectorial bond-valence sums might be used as a proxy for some aspect of structural potential energy. These results are all strictly in harmony with the VSEPR model of molecular geometry, but may allow for more quantitative prediction.
Keywords : Crystal structure; oxide; bond valence; vectorial bond-valence model; electronegativity; lone pair; second-order Jahn-Teller effect; spherical symmetry; minimum coordination number
Received: 2012-8-21
Accepted: 2012-9-17
Published Online: 2015-3-7
Published in Print: 2013-2-1
© 2015 by Walter de Gruyter Berlin/Boston
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Keywords for this article
Crystal structure;
oxide;
bond valence;
vectorial bond-valence model;
electronegativity;
lone pair;
second-order Jahn-Teller effect;
spherical symmetry;
minimum coordination number
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