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 Title: Anion photoelectron spectroscopy of NbW_ and W2_ Author(s): Schnepper, D. Alex Contributor(s): Casey, Sean M.; Leopold, Doreen; Baudhuin, Melissa A. Subject(s): Metal containing Abstract: The 488 nm vibrationally-resolved photoelectron spectra of NbW$^{-}$ and W$_{2}$$^{-} are reported. The electron affinity of W_{2} ( ^{1}$$Sigma$$_{g}$$^{+}$ $leftarrow$ $^{2}$$Sigma$$_{u}$$^{+} ) is found to be 1.118 pm 0.007 eV, which differs from the value reported in a previous anion photoelectron spectroscopic study of W_{2}$$^{-}$ (1.46 eV)footnote{H. Weidele et al., Chem. Phys. Lett. 237 (1995) 425-431}, but was accurately predicted by density functional calculations (1.12 eV)footnote{Z. J. Wu, X. F. Ma, Chem. Phys. Lett. 371 (2003) 35-39}. The fundamental vibrational frequency of W$_{2}$ is measured to be 345 $pm$ 15 wn, in agreement with the value previously reported in matrix resonance Raman studies (337 wn)footnote{Z. Hu, J.-G. Dong, J. R. Lombardi, D. M. Lindsay, J. Chem. Phys. 97 (1992) 8811-8812}. The W$_{2}$$^{-} anion is measured to have a fundamental frequency of 320 pm 15 wn. Several weak transitions to excited electronic states are seen and tentatively assigned based on calculated energies. NbW has an electron affinity of 0.856 pm 0.007 eV. Vibrational frequencies are found, by Franck-Condon fitting of overlapping transitions, to be 365 pm 20 cm^{-1} for NbW^{-} and 410 pm 20 cm^{-1} for NbW. This increase in vibrational frequency upon photodetachment suggests that the extra electron is in an antibonding orbital, leading to ground state assignments of ^{3}$$Delta$ and $^{2}$$Delta$ for the anion and neutral, respectively. These results are compared to those obtained for other Group V and Group VI transition metal dimers and trends are discussed. Issue Date: 23-Jun-15 Publisher: International Symposium on Molecular Spectroscopy Citation Info: ACS Genre: Conference Paper / Presentation Type: Text Language: English URI: http://hdl.handle.net/2142/79488 Date Available in IDEALS: 2016-01-05
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