Year: 2026
Type: preprint
Abstract: Electronegativity remains conceptually ambiguous: is it a fixed atomic constant, or does it depend on the chemical environment? We resolve this debate by recasting electronegativity as a continuous response function rooted in the Atomic Mean Inner Potential (AMIP). Building on the established static scale \(χ_{\mathrm{AMIP},1/2}\), we expand the electronegativity in fractional positive charge \(δ\). The first-order term defines the Electrostatic Rigidity \(\mathcal{R}\), whose sign indicates whether an atom hardens or softens upon oxidation, and the second-order term defines the Electrostatic Anharmonic Modulus \(\mathcal{A}\). A logarithmic-derivative decomposition separates \(\mathcal{R}\) into an intrinsic, scale-independent response asymmetry \(\mathcal{D} \equiv \mathcal{R}_Ω/Ω_0 - \mathcal{R}_f/f_0\), which governs the competition between electronic screening loss (softening) and geometric volume collapse (hardening). Applying this to all 102 elements reveals a systematic dichotomy between softening main-group elements and hardening d-block elements, two scaling laws within the transition series, and two anomalies at half-filled d\(^5\) configurations and in Ce. The framework resolves the Cs--Fr controversy through relativistic analysis, reproduces classical electronegativity scales and Lewis acidity trends, and provides three falsifiable experimental predictions. It transforms electronegativity into a predictive, hierarchically structured quantum descriptor.
Source: arXiv (Cornell University)
Author: Zheng, Jin-Cheng
Language: English
Subfield: History and Philosophy of Science
Field: Arts and Humanities
Domain: Social Sciences
Open Access status: green
Funder: Xiamen University
OpenAlex ID: W7223218937