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 Title: Structures, Energetics, And Vibrations Of Small Transition Metal Oxide Clusters By High-resolution Anion Photoelectron Spectroscopy Author(s): Kim, Jongjin B. Contributor(s): Neumark, Daniel; Weichman, Marissa L. Subject(s): Mini-symposium: Beyond the Mass-to-Charge Ratio: Spectroscopic Probes of the Structures of Ions Abstract: Anion photoelectron spectroscopy has been a major tool in understanding the vibronic structure of metal oxide clusters, due to its universality and sensitivity. However, high ion temperatures and modest photoelectron energy resolutions have hampered the observation of vibrational structure. We have recently coupled our high-resolution slow photoelectron velocity-map imaging (SEVI) spectrometer to a cryogenic ion trap and a laser ablation ion source, allowing for the acquisition of photoelectron spectra of vibrationally cold metal oxide anions with a resolution down to $\sim$4~cm$^{-1}$, limited by unresolved rotational structure. A test study of the simple $d^0$ group 4 MO$_2$ triatomic metal oxides yielded fully vibrationally-resolved spectra, allowing for reassignments of electron affinities, new measurements of vibrational fundamentals, and estimates of the anion geometries based on the observed FC structure. Studies of the corresponding Ti$_2$O$_4$ and Zr$_2$O$_4$ systems revealed vibrational progressions that allows for an unambiguous assignment of the anion isomers; previous photoelectron spectra could not distinguish the isomers based on detachment energies alone. Spectra of the VO$_2^-$ anion identified the first three electronic states of the $d^1$ neutral as well as $\nu_1$ and $\nu_2$ vibrations in each state. Issue Date: 2014-06-19 Publisher: International Symposium on Molecular Spectroscopy Citation Info: Kim, J.B.; Neumark, D.; Weichman, M.L. STRUCTURES, ENERGETICS, AND VIBRATIONS OF SMALL TRANSITION METAL OXIDE CLUSTERS BY HIGH-RESOLUTION ANION PHOTOELECTRON SPECTROSCOPY. Proceedings of the International Symposium on Molecular Spectroscopy, Urbana, IL, June 16-21, 2014. DOI: 10.15278/isms.2014.RG12 Genre: CONFERENCE PAPER/PRESENTATION Type: Text Language: English URI: http://hdl.handle.net/2142/51085 DOI: 10.15278/isms.2014.RG12 Rights Information: Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/ Date Available in IDEALS: 2014-09-172015-04-14
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