Electronic structure effects in the vectorial bond-valence model

Bickmore, Barry R.; Wander, Matthew F.C.; Edwards, Joel H.; Maurer, Joshua A.; Shepherd, Kendrick M.; Meyer, Eric; Johansen, W. Joel; Frank, Rose A.; Andros, Charles; Davis, Matthew

doi:10.2138/am.2013.4329

Cited by 18 publications

(10 citation statements)

References 43 publications

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“…In his description of a recent expansion of the BVM called the core-and-valence-shell model, Brown (2011) posited spherically symmetrical atoms in which weaker bonds tend to allow the symmetrical distribution of bonding and non-bonding (lone-pair) valence electron density, whereas strong bonds tend to make the lone pairs stereoactive, concentrating the lone-pair density to one side of the atom. Bickmore et al (2013) and quantified the resulting distortions in the coordination sphere, showing that if bonds are represented as vectors in the direction from cation to anion and magnitude equal to the bond valence, the valence dipole moment (i.e., the vectorial valence sum) and the valence quadrupole moment are predictable functions of the expected types of electronic structure effects and the magnitude of the incident bond valence. Clearly, small departures from the traditional ionic framework of the BVM can yield large dividends in terms of the ability to model the total structure of a much larger class of compounds.…”

Section: Bond Valence and Covalent Bondingmentioning

confidence: 99%

“…Such ad hoc adjustments, like dimerization, come with a cost, because they make it difficult or impossible to apply the recent extensions of the BVM that account for bond directionality (Brown 2011;Bickmore et al 2013). Bonded pairs still take up space on the surface of an atom, whether the BVM acknowledges their existence, or not.…”

Section: Bond Valence and Covalent Bondingmentioning

confidence: 99%

“…One factor affecting this spatial distribution is necessarily ligand-ligand interactions, but the BVM has traditionally been developed within a generally ionic framework, in which bonds only exist between cations and anions. If ligand-ligand interactions are treated at all within a typical BVM-based structural model, it is usually by the introduction of simple repulsive potentials (Brown 2002) or arguments based on symmetry (Brown 2006(Brown , 2011Bickmore et al 2013). Both types are likely required.…”

Section: Introductionmentioning

confidence: 99%

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The use of cation-cation and anion-anion bonds to augment the bond-valence model

Wander

Bickmore

Davis

et al. 2014

American Mineralogist

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The bond-valence model has, for several decades, been widely used for creating quantitative structure-activity relationships (QSARs), crystal structure modeling, and verification of proposed structures. Certain limitations of the model, such as the neglect of interactions between cations and between anions, have prevented it from being more broadly applied. In this work, we use cation-cation and anion-anion bonds to augment the existing bonding model in the systems H-Al-Si-O and K-Al-Si-O. The bond valence-length curves for these interactions employ the same mathematical form as ionic bonds, but make only a small contribution to the overall bonding in ionic materials. In the systems examined here, oxygen-oxygen interactions were much more important than those between cations for producing accurate bond-valence sums. Both anion-anion and cation-cation bonding could prove important, however, for our ultimate goal of producing valence-based force fields for use in molecular dynamics simulations. Rolling these interactions into the bond-valence framework would produce behavior similar to hard-sphere repulsive or van der Waals terms, but would more flexibly account for the complete bonding environment. The overall improvement in valence sums was robust, was maintained outside the calibration set, and was invariant to elemental substitution. We conclude that this minor alteration of the bond-valence approach will significantly improve bond-valence models in conjunction with other recent extensions of the approach.

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Section: Bond Valence and Covalent Bondingmentioning

confidence: 99%

Section: Bond Valence and Covalent Bondingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The use of cation-cation and anion-anion bonds to augment the bond-valence model

Wander

Bickmore

Davis

et al. 2014

American Mineralogist

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“…The vector valence sum of an atom is closely related to the slope of the valence map at the location of the atom, a zero sum indicating a minimum in the valence map. A recent study by Bickmore et al [69] shows that in cases where the bonds are not uniformly distributed, e.g., when the central atom has a stereoactive lone pair [78 section 7.1], the valence vector sum provides a convenient measure of the deviation of the atomic environment from centrosymmetric symmetry.…”

Section: The Origin and Development Of The Bond Valence Theorymentioning

confidence: 99%

Historical Introduction

Brown

2013

Structure and Bonding

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The bond valence theory grew out of Linus Pauling's electrostatic valence principle, but its development was slow until crystal structure determination became sufficiently accurate to make clear how the valence of a bond correlates with its length. Armed with this quantitative link with experiment, the theory has subsequently found many uses in analysing, modelling and predicting the structures of complex crystals, surfaces and liquids. Its theorems show how the physical properties of complex materials can be understood as the consequence of their chemical structure. The theory is increasingly finding new uses in solidstate chemistry and condensed matter physics.Keywords Bond valence Á History of bond valence Á Pauling's electrostatic valence principle Contents

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“…The concept of the scalar bond valence is also vectorized to describe the geometry of crystal structures [13,14,15].…”

Section: Introductionmentioning

confidence: 99%

Application of the bond valence method in the non-isovalent semiconductor alloy (GaN)_1−x(ZnO)_x

Liu¹

2016

Modelling Simul. Mater. Sci. Eng.

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Abstract. This paper studies the bond valence method (BVM) and its application in the non-isovalent semiconductor alloy (GaN) 1−x (ZnO)x. Particular attention is paid to the role of short-range order (SRO). The theoretical standing of BVM is examined by density-functional theory (DFT) calculations. Combining BVM with Monte-Carlo simulations and a DFT-based cluster expansion model, bond-length distributions and bond-angle variations are predicted.The connection between bond valence and bond stiffness is also discussed. Finally BVM is extended to the modelling of an interatomic potential.

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Electronic structure effects in the vectorial bond-valence model

Cited by 18 publications

References 43 publications

The use of cation-cation and anion-anion bonds to augment the bond-valence model

The use of cation-cation and anion-anion bonds to augment the bond-valence model

Historical Introduction

Application of the bond valence method in the non-isovalent semiconductor alloy (GaN)_1−x(ZnO)_x

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Electronic structure effects in the vectorial bond-valence model

Cited by 18 publications

References 43 publications

The use of cation-cation and anion-anion bonds to augment the bond-valence model

The use of cation-cation and anion-anion bonds to augment the bond-valence model

Historical Introduction

Application of the bond valence method in the non-isovalent semiconductor alloy (GaN)1−x(ZnO)x

Contact Info

Product

Resources

About

Application of the bond valence method in the non-isovalent semiconductor alloy (GaN)_1−x(ZnO)_x