LASER SPECTROSCOPY OF TiO: ACCURATE TERM ENERGIES FOR THE SINGLET STATE MANIFOLD

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1995

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Ohio State University

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The wavelength-resolved fluorescence excitation technique has been used to record the (2,0) band of the $C^{3}\Delta_{3}-a^{1}\Delta$ transition and the (2,3) and (2,4) bands of the $C^{3}\Delta_{3}-X^{3}\Delta_{3}$ electronic transition of TiO at a resolution of $0.03 cm^{-1}$. These data were combined with previous high-resolution analysis of the ground $X^{3}\Delta state^{1}$ to obtain accurate term energies for the singlet states manifold of TiO. The term energy for the first excited $a^{1}\Delta$ state above the (nonexistent) J=0 level of the $X^{3}\Delta_{1}$ ground state is: $T_{0}(a^{1}\Delta) = 3444.367\pm 0.020 cm^{-1}$. This value differs significantly from the previously derived $value^{2}$ of $T_{0}(a^{1}\Delta) = 3448.33\pm 0.04 cm^{-1}$. Energy values are lesser by about $4 cm^{-1}$ than currently accepted $values^{3}$ for the singlet states of TiO. The principal constants (in $cm^{-1}$) obtained from recent and previous analyses are: $\begin{array}{lccll}State&v&T_{v}&B_{v}&D_{v} 10^{7}\\ e^{1}\Sigma^{+}&0&29 960.592(14)&0.488 25(3)&5.10(12)\\ f^{1}\Delta&0&22 513.355(4)&0.502 363(6)&6.671(30)\\ c^{1}\Phi&0&21 284.957(4)&0.521 366(15)&3.16(13)\\ b^{1}\Pi&0&14 717.185(3)&0.511 995(6)e&6.409(25)\\ &&&0.512 154(6)f&6.425(26)\\ C^{3}\Delta_{2}&2&21 176.502(3)&0.489 124(10)&6.913\\ d^{1}\Sigma^{+}&0&5 663.147(4)&0.547 702(7)&6.3813(26)\\ a^{1}\Delta&0&3 444.367(1)&0.536 287(4)&6.107(29) \end{array}$ Work supported by AFOSR under grants F19628-90-C-025 and F49620-92-J-0215.

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1. T. Gustavsson, C. Amiot, and J. Verges, J. Mol. Spectrosc. 145, 56 (1991). 2. A.I. Kobylyanskii, A.N. Kulikov, and L.V. Gurvich, Opt. Spectrosc. 54, 244 (1983) (Engl. ed.). 3. A.J. Merer, Annu. Rev. Phys. Chem., 40, 407 (1989).
Author Institution: Emory University, Atlanta, GA 30322

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