Spectroscopic observation of jet-cooled 2,5-dichlorobenzyl radical generated by corona discharge

Vibronically excited but jet-cooled 2,5-dichlorobenzyl radical was generated from 2,5-dichlorotoluene precursor in a large excess of helium carrier gas, from which the visible vibronic emission spectrum was recorded. From an analysis of the spectrum observed, it was found that the origin band shows larger shift to red than those expected from mono-substitutions, which has been discussed in terms of orientation of substituents. Also, the electronic energy of the D1 → D0 transition and vibrational mode frequencies at the ground electronic state of the 2,5-dichlorobenzyl radical were determined in comparison with the known vibrational data of precursor and ab initio calculations.