Counterintuitive Potential-Barrier Affinity Effect

Abstract: Electron accumulation in interatomic regions is a fundamental quantum phenomenon dictating chemical bonding and material properties, yet its origin remains elusive across disciplines. Here, we report a counterintuitive quantum effect -- potential-barrier affinity (PBA) -- revealed by solving the Schrödinger equation for a crystalline potential. PBA effect drives significant interatomic electron accumulation when electron energy exceeds the barrier maximum. This effect essentially determines interatomic electron density patterns, governing microstructures and properties of condensed matters. Our theory overturns the traditional wisdom that the interstitial electron localization in electride requires potential-well constraints or hybrid orbitals, and it serves the fundamental mechanism underlying the formation of conventional chemical bonds. This work delivers a paradigm shift in understanding electron distribution and establishes a theoretical foundation for the microscopic design of material properties.