- journal_title：American Mineralogist
- Contributor：Barry R. Bickmore ; Matthew F.C. Wander ; Joel Edwards ; Josh Maurer ; Kendrick Shepherd ; Eric Meyer ; W. Joel Johansen ; Rose A. Frank ; Charles Andros ; Matthew Davis
- Publisher：Mineralogical Society of America
- Date：2013-02-01
- Format：text/html
- Language：en
- Identifier：10.2138/am.2013.4329
- journal_abbrev：American Mineralogist
- issn：0003-004X
- volume：98
- issue：2-3
- firstpage：340
- section：Article
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 simple-oxide 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.