Bond-valence theory is a general electrostatic valence rule

Pauling's electrostatic valence rule assigns to each bond of a cation of charge $z$ with $n$ anion neighbors the strength $z/n$. Bond-valence theory replaces the equal split of valence among bonds by $s=\exp[(R_0-d)/B]$ in the bond length $d$ and takes the sum rule, that the valences at each atom add to its formal charge, as its first axiom. Here the bond valence is defined in the electron density. Atomic basins of a first-principles density are bounded by faces, one per bond critical point, and the electric flux of that density through a face is a charge associated with the bond. The fluxes leaving a cation sum to its basin charge by Gauss's law, so on this surface the sum rule is a theorem. Across 3680 oxides, halides, chalcogenides and pnictides the flux follows the bond-valence law site by site, with a median deviation of ten percent. The softness $B$ varies nearly an order of magnitude from stiff sulfides to softer arsenides. In all cases it is set by the electrostatic flux at atomic basin faces. $R_0$ then follows from the bond lengths and their differences. Anion valences equal those of bonded cations to within 5\% for most of the oxide, fluoride, sulfide and nitride sites. Transferability of $(R_0,B)$ between compounds fails in 96 of 106 families, suggesting that the softness is a local site property defined by the basin charge rather than a transferable constant of a given cation--anion pair. Eliminating $B$ by the sum rule gives $s=(z/n)^{(R_0-d)/(R_0-d_B)}$, Pauling's strength raised to a distance exponent at the softness-weighted mean bond length $d_B$. Thus, bond-valence theory is Pauling's rule with a distance exponent, and the electron density supplies the surface on which the two are equivalent.

Authors

Publication Details

Journal
arXiv (Cornell University)
Published
2026-11-03
DOI
https://doi.org/10.48550/arxiv.2611.05339
Primary Topic
Advanced Chemical Physics Studies
Type
preprint
Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
preprint

Bond-valence theory is a general electrostatic valence rule

M. L. Whittaker
arXiv (Cornell University)
Advanced Chemical Physics Studies
preprint

Bond-valence theory is a general electrostatic valence rule

M. L. Whittaker
preprint en

Abstract

Pauling's electrostatic valence rule assigns to each bond of a cation of charge $z$ with $n$ anion neighbors the strength $z/n$. Bond-valence theory replaces the equal split of valence among bonds by $s=\exp[(R_0-d)/B]$ in the bond length $d$ and takes the sum rule, that the valences at each atom add to its formal charge, as its first axiom. Here the bond valence is defined in the electron density. Atomic basins of a first-principles density are bounded by faces, one per bond critical point, and the electric flux of that density through a face is a charge associated with the bond. The fluxes leaving a cation sum to its basin charge by Gauss's law, so on this surface the sum rule is a theorem. Across 3680 oxides, halides, chalcogenides and pnictides the flux follows the bond-valence law site by site, with a median deviation of ten percent. The softness $B$ varies nearly an order of magnitude from stiff sulfides to softer arsenides. In all cases it is set by the electrostatic flux at atomic basin faces. $R_0$ then follows from the bond lengths and their differences. Anion valences equal those of bonded cations to within 5\% for most of the oxide, fluoride, sulfide and nitride sites. Transferability of $(R_0,B)$ between compounds fails in 96 of 106 families, suggesting that the softness is a local site property defined by the basin charge rather than a transferable constant of a given cation--anion pair. Eliminating $B$ by the sum rule gives $s=(z/n)^{(R_0-d)/(R_0-d_B)}$, Pauling's strength raised to a distance exponent at the softness-weighted mean bond length $d_B$. Thus, bond-valence theory is Pauling's rule with a distance exponent, and the electron density supplies the surface on which the two are equivalent.

arXiv (Cornell University)
Advanced Chemical Physics Studies
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.

Laika access coming soon
Bond-valence theory is a general electrostatic valence rule — M. L. Whittaker · arXiv (Cornell University) (2026) | TGRS Research Map | TGRS