Multi-Equalization in Conceptual Density Functional Theory: Beyond Electronegativity Equalization

Physics > Chemical Physics [Submitted on 17 Jun 2026] Title:Multi-Equalization in Conceptual Density Functional Theory: Beyond Electronegativity Equalization View PDFAbstract:The electronegativity equalization principle provides a simple framework to describe charge redistribution, yet its conventional formulation is limited to a first-order description based on chemical potential equalization. In this work, we introduce 'multi-equalization,' a generalized framework that extends this concept by incorporating higher-order responses within Conceptual Density Functional Theory. This approach represents molecules as sets of flexible electron density partitions, allowing different electronic descriptions (e.g., atomic densities or localized orbitals) to be treated within a unified formalism. We demonstrate that correlations between energy and density derivatives with respect to the number of electrons lead to the simultaneous equalization of multiple descriptors, including chemical hardness and Fukui indices. A constructive algorithm is introduced to determine the optimal density partitions satisfying these multi-equalization conditions. This scheme provides a consistent description of both global charge transfer and local reactivity, overcoming the intrinsic limitations of traditional electronegativity equalization models. Notably, the inclusion of density response functions enables local hardness equalization, introducing spatial resolution into reactivity descriptions. Under multi-equalization, local reactivity descriptors become constrained functionals of the global electron density. This framework establishes a deeper connection between charge equalization models and formal density functional theory, offering a theoretically grounded route toward improved predictions of molecular reactivity. Submission history From: Jesús Sánchez-Márquez [view email][v1] Wed, 17 Jun 2026 19:38:37 UTC (3,125 KB) Current browse context: physics.chem-ph Change to browse by: References & Citations Loading... Bibliographic and Citation Tools Bibliographic Explorer (What is the Explorer?) Connected Papers (What is Connected Papers?) Litmaps (What is Litmaps?) scite Smart Citations (What are Smart Citations?) Code, Data and Media Associated with this Article alphaXiv (What is alphaXiv?) CatalyzeX Code Finder for Papers (What is CatalyzeX?) DagsHub (What is DagsHub?) Gotit.pub (What is GotitPub?) Hugging Face (What is Huggingface?) ScienceCast (What is ScienceCast?) Demos Recommenders and Search Tools Influence Flower (What are Influence Flowers?) CORE Recommender (What is CORE?) arXivLabs: experimental projects with community collaborators arXivLabs is a framework that allows collaborators to develop and share new arXiv features directly on our website. Both individuals and organizations that work with arXivLabs have embraced and accepted our values of openness, community, excellence, and user data privacy. arXiv is committed to these values and only works with partners that adhere to them. Have an idea for a project that will add value for arXiv's community? Learn more about arXivLabs.