Infrared spectra of TiO2 clusters for hot Jupiter atmospheres

Abstract

Context. Clouds seem unavoidable in cool and dense environments, and hence, are necessary to explain observations of exoplanet atmospheres, most recently of WASP 96b with JWST. Understanding the formation of cloud condensation nuclei in non-terrestrial environments is therefore crucial to develop accurate models to interpret present and future observations. Aims. The goal of the paper is to support observations with infrared spectra for (TiO2)N clusters in order to study cloud formation in exoplanet atmospheres. Methods. Vibrational frequencies are derived from quantum-chemical calculations for 123 (TiO2)-clusters and their isomers, and line-broadening mechanisms are evaluated. Cluster spectra are calculated for several atmospheric levels for two example exoplanet atmospheres (WASP 121b-like and WASP 96b-like) to identify possible spectral fingerprints for cloud formation. Results. Rotational motion of and transitions in the clusters cause significant line broadening, so that individual vibrational lines are broadened beyond the spectral resolution of the medium resolution mode of the JWST mid-infrared instrument MIRI at R = 3000. However, each individual cluster isomer exhibits a "fingerprint" IR spectrum. In particular, larger (TiO2)-clusters have distinctly different spectra from smaller clusters. Morning and evening terminator for the same planet can exhibit different total absorbances due to different cluster sizes being more abundant. Conclusions. The largest (TiO2)-clusters are not necessarily the most abundant (TiO2)-clusters in the high-altitude regions of ultra-hot Jupiters, and the different cluster isomers will contribute to the local absorbance. Planets with a considerable day-night asymmetry will be most suitable to search for (TiO2)-cluster isomers in order to improve cloud formation modelling.