LASER PHOTOLUMINESCENCE OF TiO IN Ne AT $4^{\circ} K$
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Date
1975
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Ohio State University
Abstract
Pseudo-gas phase photoluminescence spectra of TiO isolated In Ne matrices at $4^{\circ} K$ have been observed. Photoluminescence was induced by laser excitation from the $X^{3}\Delta$ ground state to $B^{3}\Pi$ and $C^{3}\Delta$ vibronic levels using a cw Tunable dye laser and a cu argon ion laser, respectively. Red emission from $B^{3}\Pi$ vibronic levels terminating in ground state levels was observed. In addition, the $B^{3}\Pi$ ($v = 0$) and $B^{3}\Pi$($v = 1$) levels have been found to undergo matrix-induced Intersystem relaxation into the $b^{1}\Pi$ state. Near-infrared emission between excited states in the singlet manifold of TiO has been observed and identified as belonging to $\delta(b^{1}\Pi a^{1}\Delta$) and $\phi( b^{1}\Pi - d^{1}\Delta^{+}$) band systems. Observed $\delta$ and $\phi$ emission bands are uniformly shifted by $-93 cm^{-1}$ and $+73 cm ^{-1}$, respectively, from observed or predicted gas phase band heads. The line shape of the $\delta$ and $\phi$ vibronic emission in the solid is that of a sharp zero-phonon line accompanied by a broad multiphonon sideband. An additional sharp zero-phonon emission system, here labeled the $\xi$ system,was found to overlap severlap several broad multiphonon bands of the red $\gamma^{\prime}(B^{3}\Pi\rightarrow X^{3}\Delta$) emission. Evidence obtained indicates that the $\xi$ system is due to intercombination $B^{1}\Pi\rightarrow X^{3}\Delta$ emission. From the assigned intercombination transition the energy of the low-lying a $^{1}\Delta$ a state is determined to e $3500 cm^{-1}$ above the $X^{3}\Delta$ ground state. The $3500 cm^{-1}$ value for the relative energy between the isoconfigurational $a^{3}\Delta$ and $X^{3}\Delta$ states is in qualitative agreement with theoretical expectations based on consideration of the bonding in the TiO molecule.
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Author Institution: Department of Physics and Quantum Institute, University of California