The ?IIou ?X ???g band system of jet-cooled Ti?

Journal ArticleA band of jet-cooled ??Ti? has been located in the near infrared by resonant two-photon ionization spectroscopy. Rotational analysis has shown the band to be an ?? =O* ???=1 transition, which is consistent with the 3??g, ground state proposed by Bauschlicher ef al. [J. Chem. Phys. 95, 1057 ( 1991)]. The band is assigned as a 3II0u ? X 3??g, transition, tnd lower and upper state bond lengths have been determined as r0(X 3?g) = 1.9422?0.0008 ? and rO( 31u,) = 1.997 ? 0.009 ? (l? error limits, corrected for spin-uncoupling effects). Comparisons are made to the TN and V, molecules, a rationale for the unusual filling order of the 3d-based molecular orbitals is provided, and molecular orbital assignments are considered for the excited 3IIu state