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

Journal Article · Fri Nov 07 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4900646· OSTI ID:22310784

Kim, Jongjin B.; Weichman, Marissa L.

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.

• OSTI ID: 22310784
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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