Volume 217, 2019

Photoelectron spectra of Al2O2 and Al3O3via slow electron velocity-map imaging

Abstract

High-resolution photoelectron spectra of cryogenically-cooled Al2O2 and Al3O3 cluster anions are obtained using slow electron velocity-map imaging. These spectra show vibrationally-resolved detachment from the ([X with combining tilde]2B3u) ground state of Al2O2 to the [X with combining tilde]1Ag and ã3B3u neutral electronic states, giving an electron affinity of 1.87904(4) eV for neutral Al2O2 and a term energy of 0.4938(4) eV for the triplet excited state. Additionally, there is evidence for autodetachment from photoexcited anions as well as influences from vibronic coupling between excited states of the neutral Al2O2 cluster. Detachment from both the “kite” and “book” isomers of Al3O3 is observed, yielding electron affinities of 2.0626(4) and 2.792(3) eV for the corresponding neutral isomers. Experiments carried out at different anion temperatures suggest that the two anionic isomers are nearly isoenergetic but clearly identify the kite isomer as the global minimum structure, in contrast to prior studies. This finding is supported by density functional theory calculations, which show that the relative ordering of the anion isomers is sensitive to basis set size; calculations for the anion isomers at the B3LYP/aug-cc-pVQZ level find the kite isomer to lie 0.011 eV below the book isomer.

Graphical abstract: Photoelectron spectra of Al2O2− and Al3O3−via slow electron velocity-map imaging

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
05 nov 2018
Accepted
29 nov 2018
First published
29 nov 2018

Faraday Discuss., 2019,217, 235-255

Author version available

Photoelectron spectra of Al2O2 and Al3O3via slow electron velocity-map imaging

J. A. DeVine, M. C. Babin and D. M. Neumark, Faraday Discuss., 2019, 217, 235 DOI: 10.1039/C8FD00165K

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