A STUDY OF NbMo AND NbMo$^{-}$ BY ANION PHOTOELECTRON SPECTROSCOPY

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2012

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Ohio State University

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We report the 488 and 514 nm anion photoelectron spectra of NbMo$^{-}$. R2PI spectroscopic studies have established that neutral NbMo has a $^{2}\Delta_{5/2}$ ground state and a short bond length . We find that the NbMo$^{-}$ anion has a $^{1}\Sigma^{+}$ ground state in which the "extra" electron occupies the (4d)$\delta$ bonding orbital, giving a $1\sigma^{2}1\pi^{4}1\delta^{4}2\sigma^{2}$ valence electron configuration. Thus, NbMo$^{-}$ has a formal bond order of 6, and is isoelectronic with Mo$_2$. Low-lying excited states of NbMo ($^{2}\Sigma^{+}$) and NbMo$^{-}$ ($^{3}\Delta$) are also observed. The spectra provide the electron affinity of NbMo, energies of the $^{2}\Sigma^{+}$ and $^{3}\Delta$ excited states, vibrational frequencies in the anion and neutral molecule ground states and the $^{2}\Sigma^{+}$ state, $^{2}\Delta$ and $^{3}\Delta$ spin-orbit splittings, and (from Franck-Condon analyses) bond length measurements for the anion ground state and the observed excited states. These results are compared with previous anion photoelectron spectroscopic data for the Group 5/6 congeners VCr and VMo, and with density functional theory predictions.

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Author Institution: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455

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