Molecular Transferability of a Noble-Gas Coordinate for Electronegativity Equalization
Abstract
Charge-equilibration models predict how electrons redistribute over a molecule more cheaply than quantum chemistry, and each begins from a table of atomic electronegativities and hardnesses. A recent table replaces ionization energies and electron affinities with one geometric quantity: each main-group atom's fractional distance to the noble gas closing its row. Holding geometries, electrostatic damping and the molecule list fixed, we compare it with spectroscopic values, with its own kernel refitted, and with a quadratic control, over a primary set of fifty-two molecules and ions at the B3LYP/def2-TZVP level. Two structural consequences follow from the table construction rather than the equalization solver. Atoms at equal fractional distance receive identical electronegativities, so the dipole moments of chlorine monofluoride, iodine monobromide and sulfur dioxide vanish exactly, and the measured $0.72$ debye HF/HCl gap is lost. Because the first period is excluded, hydrogen retains its spectroscopic electronegativity above every geometric value, reversing O−H, N−H and hydrogen-halide polarity. Fitted alike, geometric and quadratic kernels agree to $0.0022$ electron per atom, so predictions are set by the fitted energy scales, not the kernel shape. Resolving the electronegativity scale period by period restores correct polarity in all five polyatomic heavy-atom-hydrogen tests.
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BibTeX
@misc{simons2026molecular,
title = {{Molecular Transferability of a Noble-Gas Coordinate for Electronegativity Equalization}},
author = {Megan Simons and Jonathan Washburn and Elshad Allahyarov},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.02930},
eprint = {2609.02930},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.02930},
}
RIS
TY - UNPB
TI - Molecular Transferability of a Noble-Gas Coordinate for Electronegativity Equalization
AU - Megan Simons
AU - Jonathan Washburn
AU - Elshad Allahyarov
PY - 2026
DA - 2026/09/01
PB - arXiv
DO - 10.48550/arxiv.2609.02930
UR - https://arxiv.org/abs/2609.02930
AB - Charge-equilibration models predict how electrons redistribute over a molecule more cheaply than quantum chemistry, and each begins from a table of atomic electronegativities and hardnesses. A recent table replaces ionization energies and electron affinities with one geometric quantity: each main-group atom's fractional distance to the noble gas closing its row. Holding geometries, electrostatic damping and the molecule list fixed, we compare it with spectroscopic values, with its own kernel refitted, and with a quadratic control, over a primary set of fifty-two molecules and ions at the B3LYP/def2-TZVP level. Two structural consequences follow from the table construction rather than the equalization solver. Atoms at equal fractional distance receive identical electronegativities, so the dipole moments of chlorine monofluoride, iodine monobromide and sulfur dioxide vanish exactly, and the measured $0.72$ debye HF/HCl gap is lost. Because the first period is excluded, hydrogen retains its spectroscopic electronegativity above every geometric value, reversing O−H, N−H and hydrogen-halide polarity. Fitted alike, geometric and quadratic kernels agree to $0.0022$ electron per atom, so predictions are set by the fitted energy scales, not the kernel shape. Resolving the electronegativity scale period by period restores correct polarity in all five polyatomic heavy-atom-hydrogen tests.
ER -