The Electronic Transition Moment Function for the B3Π–X3Δ System of TiO

✍ Scribed by Kei-ichi C. Namiki; Haruhiko Ito

• Publisher: Elsevier Science
• Year: 2002
• Tongue: English
• Weight: 136 KB
• Volume: 214
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1006/jmsp.2002.8586

✦ Synopsis

Several vibronic bands associated with v = 0, 1, and 2 for the B 3 -X 3 transition of TiO have been observed using a dispersed laser induced fluorescence (DLIF) technique. From intensity distributions of the DLIF spectra, the dependence of the electronic transition moment R e (r ) for the B 3 -X 3 system was determined as a function of the internuclear distance r . For the determination of the R e (r ) function, a merged fit of the observed distributions, the reported radiative lifetimes of three vibrational levels in the B 3 state, and the reported value of R e (r ) for the (0, 0) band were performed; R e (r ) was determined as R e (r ) = 1.3723(79)[1 -0.316(81)(rr 0 ) + 2.0(10)(rr 0 ) 2 ](r 0 = 1.6648 Å and 1.5131 Å ≤ r ≤ 1.8636 Å). The r-dependence of R e (r ) was much smaller than the reported theoretical predictions. The obtained values of R e (r ) were analyzed simultaneously with the hyperfine coupling constants for the X 3 state and the spin-orbit constants for the X 3 and B 3 states to assess the ionic and orbital characters. It was found that the r-dependence of R e (r ) could be accounted for by both the configuration interaction in the B 3 state and the polarization in the unpaired 9σ and 4π orbitals.