Abstract
The dissociative chemisorption of heteronuclear molecules is a cornerstone of heterogeneous catalysis. However, the ability to predict and control how rotational excitation governs reactivity has remained a fundamental challenge, lagging far behind the established understanding of vibrational effects. Here, through six-dimensional quantum dynamics simulations of HCl dissociation on bimetallic surfaces, we report unprecedented rotational enhancement, with efficacies reaching roughly 225 and 56 on Ag/Pt(111) and Cu/Pt(111), respectively. This dramatic effect originates from interfacial charge transfer driven by work function differences between the substrate and the supported metal monolayer (Φ (sub) > Φ (sup)), which generates a non-monotonic orientation-dependent potential energy landscape. We further establish a quantitative, predictive design principle, where rotational efficacy scales primarily with the work function difference and is systematically modulated by surface strain, with the highest efficacy achieved when a large work function difference is combined with compressive strain. This multivariate framework resolves a long standing dichotomy by demonstrating that rotational effects depend decisively on the global topography of the potential energy surface (PES), a mechanism fundamentally distinct from the transition state (TS) localized picture of vibrational promotion. The resulting quantum state control window enables rotation to act as a precise external knob for steering reactivity, advancing a new paradigm for the design of catalysts with targeted, state selective function.