Polarization‐resolved (2+1) resonance‐enhanced multiphoton ionization spectroscopy of CF3I (6s) Rydberg states

Craig A. Taatjes, Johanna W. G. Mastenbroek, Ger van den Hoek, Jaap G. Snijders, Steven Stolte
1993 Journal of Chemical Physics  
The CF,I( 5pr-6s) Rydberg transitions in the energy range 56 700-64 000 cm-' are investigated using (2+ 1) resonance-enhanced multiphoton ionization. The polarization of the twophoton transitions is used to definitely assign the symmetries of the resonant intermediate states. The four allowed electronic transitions in the (5p~--6s) manifold have been assigned and some vibrational constants in the excited states have been determined. Hot band spectra have been obtained in a supersonic expansion
more » ... f CF,I through an oven. The upper spin-orbit components (the 2E1,2 ion core states) are perturbed by a dissociative state at approximately 63 000 cm-', possibly the (T-O* transition centered on the C-I bond. Density functional calculations have been performed in order to help determine the nature of the perturbing states. Vibronic interactions in the excited states are investigated, and evidence is seen for quadratic Jahn-Teller interactions for y6 in the lower (2E3,2> spin-orbit state.
doi:10.1063/1.464997 fatcat:uvkmm2b7wjfedd22qkm54e5rne