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Title: Slow photoelectron velocity-map imaging spectroscopy of the Fe{sub 3}O{sup –} and Co{sub 3}O{sup –} anions

We report high-resolution photoelectron spectra of the transition metal suboxide clusters Fe{sub 3}O{sup −} and Co{sub 3}O{sup −}{sub .} The combination of slow electron velocity-map imaging and cryogenic cooling yields vibrationally well-resolved spectra, from which we obtain precise values of 1.4408(3) and 1.3951(4) eV for the electron affinities of Fe{sub 3}O and Co{sub 3}O. Several vibrational frequencies of the neutral ground state Fe{sub 3}O and Co{sub 3}O clusters are assigned for the first time, and a low-lying excited state of Fe{sub 3}O is observed. The experimental results are compared with density functional electronic structure calculations and Franck-Condon spectral simulations, enabling identification of the structural isomer and electronic states. As has been found in photoelectron spectra of other trimetal oxo species, Fe{sub 3}O{sup 0/−} and Co{sub 3}O{sup 0/−} are assigned to a μ{sub 2}-oxo isomer with planar C{sub 2v} symmetry. We identify the ground states of Fe{sub 3}O{sup –} and Co{sub 3}O{sup –} as {sup 12}A{sub 1} and {sup 9}B{sub 2} states, respectively. From these states we observe photodetachment to the {sup 11}B{sub 2} ground and {sup 13}A{sub 1} excited states of Fe{sub 3}O, as well as to the {sup 8}A{sub 1} ground state of Co{sub 3}O.
Authors:
; ;  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22310784
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 17; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; COOLING; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; ELECTRONS; EXCITED STATES; GROUND STATES; ISOMERS; PHOTOELECTRON SPECTROSCOPY; SIMULATION; SPECTRA; TRANSITION ELEMENTS