STRONG VIBRONIC COUPLING IN THE VISIBLE SPECTRUM OF ZIRCONIUM METHYLIDYNE

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2003

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Ohio State University

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Zirconium methylidyne, ZrCH, can be prepared by the reaction of methane (8% in helium) with laser-ablated zirconium atoms. At least 50 vibrational bands have been observed in the $565 - 665$ nm region for each of ZrCH and ZrCD using laser-induced fluorescence. Dispersed emission spectra have allowed the assignment of numerous excited vibrational levels in the $\tilde{X}^{2}\Sigma^{+}$ ground state (17 for ZrCH, 22 for ZrCD and 9 for $Zr^{13}CH$). The ground state bond lengths, as determined from high-resolution spectra of ZrCH and ZrCD, are $r_{0}(Zr-C) - 1.83067(13) {\AA}$ and $r_{0}(C-H)= 1.0866(9) \AA$. $P^{\prime}$ values derived from rotational analyses of 20 subbands in the electronic spectrum (9 of ZrCH and 11 of ZrCD) reveal a very complicated level structure. Preliminary vibrational assignment suggests the presence of two interacting excited states, $^{2}\Pi$ and $^{2}\Delta$, about $250 cm^{-1}$ apart. Many vibronically-induced bands consequently appear with unusual properties such as anomalous branch intensity patterns or upper levels with very large electrostatic (Renner-Teller) splittings between their angular momentum components.

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$^{a}$ Present address: Creo Inc., 3755 Willingdon Avenue, Burnaby, BC, Canada V5G 3H3
Author Institution: Department of Chemistry, University of British Columbia; Department of Physics and Astronomy, University of British Columbia

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