Resolved (v₁, v₂ = 1) Combination Vibrational States of CF₃ Fragments in the Photofragment Translational Spectra of CF₃I

Abstract

The photodissociation of CFI → CF(v,v) + I*/I has been investigated at 248, 266, and 277 nm with our high resolution mini-TOF photofragment translational spectrometer. Based on the theoretical calculations of Clary and of Bowman et al., now in this manuscript, we assign 701 cm to the CF symmetric stretch (breathing) ν mode, and 1086 cm to the umbrella ν mode of the CF fragment. In the obtained TOF spectra of I from the I* channel, situated in the 701 cm gaps between the original series of (v, 0) vibrational peaks, a new series of weaker (v, 1) vibrational peaks are partially resolved. These observed new peaks with 1086 cm ν mode excitation have never been reported in previous literature. In the TOF spectra of I from the I channel, the new series of (v, 1) peaks are also partially resolved. However, these spectra of I channel are less satisfactory, because for higher E and higher E, the higher resolution of PTS is required. The potential energy at the curve crossing point and the excitation of CF (v, 2) and (v, 3) vibrational states have been also analyzed.

Molecular photodissociation dynamics revealed by Coulomb explosion imaging

“…a UV = ultraviolet pump wavelength, X = XUV or X-ray, NIR = near infrared. (dt B 1 ns) all match well, support previous conclusions that most (490%) of the iodine atoms formed following excitation of CF 3 I molecules at 267 nm are in the spin-orbit excited ( 2 P 1/2 ) rather than ground ( 2 P 3/2 ) state (henceforth identified as I* and I, respectively) [201][202][203] and imply similar NIR SFI probabilities for both spin-orbit states of the I atom.…”