Revealing SO2 and CO2 adsorption features on forsterite via IR spectroscopy and automated computational approaches†

The interaction between interstellar molecules and silicate dust plays a critical role in the chemical evolution of interstellar and circumstellar environments. In this work, we combine in situ infrared (IR) spectroscopy with automated density functional theory (DFT) calculations to investigate the adsorption and vibrational signatures of CO₂ and SO₂ on forsterite surfaces. Experimental IR spectra collected under cryogenic conditions reveal coverage- and temperature-dependent features that evolve from physisorbed to chemisorbed regimes. To interpret these observations, we construct theoretical spectra from a large ensemble of adsorption configurations across multiple surface terminations, weighted by their Boltzmann distributions at 100 K and by a per-surface abundance factor. The resulting spectra reproduce key experimental features, enabling the identification of binding trends. For CO₂, we predict the transition from weakly bound species to carbonate-like modes at lower frequencies. For SO₂, our simulations identify the dominant bands due to bidentate and tridentate chemisorption. This integrative approach highlights the importance of surface morphology and thermodynamic weighting in reconciling theory and experiments providing a framework for the spectroscopic analysis of molecular adsorption on interstellar dust analogs.