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Anion photoelectron spectroscopy of NbW_ and W2_
The 488 nm vibrationally-resolved photoelectron spectra of NbW and W are reported. The electron affinity of W ( ) is found to be 1.118 0.007 eV, which differs from the value reported in a previous anion photoelectron spectroscopic study of W (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 is measured to be 345 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 anion is measured to have a fundamental frequency of 320 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 0.007 eV. Vibrational frequencies are found, by Franck-Condon fitting of overlapping transitions, to be 365 20 cm for NbW and 410 20 cm 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 and 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