Vibronic structure of VO{sub 2} probed by slow photoelectron velocity-map imaging spectroscopy
We report high-resolution anion photoelectron spectra of vanadium dioxide (VO{sub 2}{sup −}) obtained by slow electron velocity-map imaging of trapped and cryogenically cooled anions. Vibrationally resolved spectra are obtained for photodetachment to the first three neutral electronic states, giving an electron affinity of 1.8357(5) eV for the X-tilde{sup 2} A{sub 1} ground state and term energies of 0.1845(8) eV and 0.8130(5) eV for the A-tilde{sup 2}B{sub 1} and B-tilde{sup 2}A{sub 1} excited states, respectively. The vibrational fundamentals ν{sub 1} and ν{sub 2} are obtained for all three states. Experimental assignments are confirmed by energies from electronic structure calculations and Franck-Condon spectral simulations. These simulations support assigning the anion ground state as the X-tilde{sup 3}B{sub 1} state. With this assignment, photodetachment to the B-tilde{sup 2}A{sub 1} state involves a nominally forbidden two-electron transition, suggesting extensive configuration interaction in neutral VO{sub 2}.
- OSTI ID:
- 22255265
- Journal Information:
- Journal of Chemical Physics, Vol. 140, Issue 3; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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