Abstract
High-resolution photoelectron spectra of cryogenically cooled TiO2CH3OH− anions obtained with slow electron velocity-map imaging are reported and explore the reactions of TiO2-/0 with methanol. The highly structured spectra were compared with results from DFT calculations to determine the dominant structure to be cis-CH3OTi(O)OH−, a dissociative adduct in which the CH3OH is split by the TiO2−. The experiment yields an electron affinity of 1.2152(7) eV for TiO2CH3OH as well as several vibrational frequencies for the neutral species. Comparison to Franck-Condon (FC) simulations shows that while most experimental features appear in the simulations, several do not and are assigned to FC-forbidden transitions involving non-totally symmetric vibrational modes. The FC-allowed and forbidden transitions also exhibit different photoelectron angular distributions. The FC-forbidden transitions are attributed to Herzberg-Teller (HT) coupling with the A ̃^2 A^'' excited state of the anion. The results are compared to previous cryo-SEVI studies of bare TiO2− and the water-split adduct TiO3H2−.
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