A predictive descriptor for the d-band center in intermetallic alloys accelerates the design of robust molecular switches

Abstract

Breaking the trade-off between stability and switching functionality remains a pivotal challenge in substrate-supported molecular switches. Herein, we propose a design strategy using A₃B-type intermetallic alloys as substrates to realize a hybrid-bonding precursor state that concurrently achieves robust interfacial stability and enhanced current-switching ratios. We demonstrate that this bistability can be directly predicted from the atomic covalent radius and d-band centers of surface metals. Remarkably, we uncover a distinctive V-shaped relationship between the d-band center of the host metal and valence electron number of the guest metal, governed by the occupancy of d–d anti-bonding states. Furthermore, we elucidate the essential role of geometric and quantum primogenic effects in modulating d–d orbital interactions, resolving longstanding controversies regarding d-band modulation mechanisms for alloys. By incorporating intrinsic parameters, including the valence electron number, atomic radius, and orbital radius of guest metals, we develop a generalizable descriptor for accurately predicting the d-band center of host metals (R² > 0.90). This work not only accelerates the exploration of robust room-temperature molecular switches, but also establishes a rational design framework for high-performance intermetallic substrates with optimal adsorption properties, thereby significantly reducing reliance on costly density functional theory calculations.