A Density-Matrix Framework for Electronic-Structure Analysis of Functional-Group and Salt Effects in Lithium-Metal Electrolytes

Abstract:The reactivity of lithium-metal electrolytes arises from the interplay of molecular functional groups, Li$^+$ solvation, and salt-anion participation. This interplay operates through the redistribution of electron density across donor, anion, and cation centers, which is most directly read out from the electronic structure resolved in space. Quantum-chemical calculations deliver such readouts faithfully, yet become computationally demanding across this multidimensional design space, and machine-learning electronic-structure models seldom cover chemically diverse solvation shells or electrolyte-relevant readouts. Here, we present a density-matrix-centered AI platform (EMolStudio) for electronic-structure prediction and analysis. Its workflow integrates molecular functionalization, explicit Li$^+$ first-shell assembly, density-matrix prediction with idempotency projection, and readouts of frontier orbitals, electrostatic potential, Li$^+$-donor bond order, and electron localization. We apply EMolStudio to 163,655 functionalized molecules and 22,500 explicit Li$^+$ first-shell clusters across four lithium salts. We find that 1) at the molecular scale, functionalization distinguishes CO$_2$Me, CN, F/CF$_3$, and sulfonyl groups by chemically distinct changes in frontier levels, electrostatic potential, and Li$^+$-donor contact, consistent with $\pi^*$-acceptor, inductive, and polarization contributions, with sublinear accumulation at higher degrees of functionalization; 2) in explicit solvation shells, anion identity reshapes frontier-orbital localization: LiTDI anchors the HOMO on the anion across the entire library, whereas LiDFOB pairs an anion-hosted HOMO with strongly functional-group-dependent LUMO hosting. EMolStudio thereby translates functional-group and salt choices into electronic-structure hypotheses relevant to lithium-bond formation, desolvation, and interphase reactions.

Artificial Intelligence (cs.AI)

arXiv:2607.25597 [cs.AI]

(or arXiv:2607.25597v1 [cs.AI] for this version)

https://doi.org/10.48550/arXiv.2607.25597 Focus to learn more arXiv-issued DOI via DataCite (pending registration)

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.