Structure and Spectroscopy of Criegee Intermediates in Gas‐ and Aqueous Environments

ABSTRACT The dynamics and spectroscopy of the small (H 2 COO) and large (CH 3 CHOO) Criegee intermediates (CIs) in the gas phase, inside/on water droplets, on amorphous solid water (ASW) and in bulk water are investigated using validated energy functions. For both species, facile diffusion between surface and inside positions for water droplets is found, whereas on amorphous solid water at low temperatures (50 K) no surface diffusion is observed on the multiple‐nanosecond time scale. This is at variance with other species, such as CO or NO on ASW. The infrared spectroscopy of both CIs in contact with an aqueous environment leads to shifts of the spectral features on the order of a few to a few tens of , depending on the vibrational mode considered. This is consistent with Stark‐induced spectral shifts for small molecules in protein environments. However, the spectroscopy of both CIs in contact with water droplets does not depend on the positioning relative to the droplet (inside vs. surface).