Reinvestigation of the Rydberg W1Π(ν = 1) level of 12C16O, 13C16O, and 12C18O through rotationally dependent photodissociation branching ratio measurements.
2020
A recent high resolution photoabsorption study revealed that the Rydberg W1Π(ν = 1) level of carbon monoxide (CO) is perturbed by the valence E″1Π(ν = 0) level, and the predissociation linewidth shows drastic variation at the crossing point due to the interference effect [Heays et al., J. Chem. Phys. 141(14), 144311 (2014)]. Here, we reinvestigate the Rydberg W1Π(ν = 1) level for the three CO isotopologues, 12C16O, 13C16O, and 12C18O, by measuring the rotationally dependent photodissociation branching ratios. The C+ ion photofragment spectra obtained here reproduce the recent high resolution photoabsorption spectra very well, including the presence of the valence E″1Π(ν = 0) level. The photodissociation branching ratios into the spin-forbidden channel C(1D) + O(3P) show sudden increases at the crossing point between the W1Π(ν = 1) and E″1Π(ν = 0) levels, which is in perfect accordance with the drastic variation of the linewidth observed in the recent spectroscopic study. Further analysis reveals that the partial predissociation rate into the lowest channel C(3P) + O(3P) shows a much more prominent decrease at the crossing point, which is caused by the interference effect between the W1Π(ν = 1) and E″1Π(ν = 0) levels, than that into the spin-forbidden channel C(1D) + O(3P), and this is the reason of the sudden increase as observed in the photodissociation branching ratio measurements. We hope that the current experimental investigation will stimulate further theoretical studies, which could thoroughly address all the experimental observations in a quantitative way.
Keywords:
- Correction
- Source
- Cite
- Save
- Machine Reading By IdeaReader
48
References
2
Citations
NaN
KQI