A Spatially‐Resolved Approach via Quantifying the Dominant Yet Overlooked Orbital‐Weighted Energy Contribution for Breaking Solvent Oxidation Chemistry

Abstract

Rational design of solvents with high oxidation chemistry stability represents an essential path toward pursuing high‐energy‐density batteries. Conventional methods assess oxidation stability using orbital energy level/ionization energetics; however, they misjudge the local nature of electron loss by ignoring the influence of collective orbitals on electron energy. Herein, we propose a spatially‐resolved energetics approach called Pseudo‐Eox, where the core average local ionization energy minimum parameter is used to measure the vulnerability of the highest‐energy electron via electron‐density‐weighted orbital energy averaging and to pinpoint its prevalent sub‐HOMO localization. This approach reproduces the oxidation stability trend of HOMO‐dominant solvents (EC/PC with quantified contributions > 60%), while mechanistically revealing why conventional models fail in most cases like DEC with HOMO contribution < 24%. Its robustness is demonstrated on 20 regular solvents with mean absolute error of only 0.38 V. Following this, taking potentially practical fluorinated solvents as a prototype, we retrieve the 2‐fluoroethyl 2,2,2‐trifluoroethyl, which will be overlooked by HOMO‐based rankings, exhibiting the highest theoretical oxidation stability (6.45 V) among candidates obtained by constructing 147 widely adopted carbonate/ether derivatives. This study overturns the single‐orbital‐only cognition of solvent oxidation, offering a spatially informed energetics perspective for investigating organic chemistry where localized electron loss governs stability and functionality.