Polymorphs are distinct structural forms of the same compound and offer unique opportunities to tailor material properties without altering chemical composition. In particular, the polymorphs of WO3 have been widely explored for their molecular sensing performance; yet, the mechanistic aspects behind their different chemoresistive properties have remained elusive or poorly understood. Here, we highlight the energetic allocation of transferred charge as a critical aspect for chemoresistive response generation, providing a new perspective beyond more conventional net-transfer metrics, which are usually deployed to investigate gas-solid interactions. To this, we combined operando work function, chemisorption analysis, and in situ spectroscopy with density functional theory calculations on the example of acetone. Both γ- and ε-WO3 exhibit comparable surface-level activation of acetone, mediated by electron-deficient, coordinatively unsaturated tungsten sites. However, only ε-WO3 stabilizes analyte-induced electronic states derived from W(5d) orbitals lying just below the conduction band-an energetically favorable region for conductivity modulation under operating conditions. While being associated with marginal work function shifts, these states reflect deeper subsurface electronic rearrangements that may underlie the ε-WO3's superior transduction efficiency despite similar receptor chemistry. Our results offer a new framework for rational transducer development rooted in intrinsic electronic structure.
D'Andria et al. (2026) studied this question.