Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiOH anions is used to probe the simplest titania/water reaction, TiO + HO. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH) geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH). The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO indicates that reaction with water stabilizes neutral TiO more than the anion, providing insight into the fundamental chemical interactions between titania and water.
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