Jet cooled emission spectra of toluene and the benzyl radical

Alkyl Group Dissociation During Corona Excitation of Alkylbenzenes

“…The strong bands at 21476 and 21384 cm -1 belong to the 6a 1 0 and 6b 1 0 bands of the benzyl radical, respectively. 3 The intensity of the origin band is lower than those of the 6a 1 0 and 6b 1 0 bands due to the selection rule. For benzyl-type radicals with substituents, the origin band always shifts to red region because of the larger space available for delocalized π electrons.…”

“…2 The benzyl radical, the prototypical aromatic free radical, is regarded to be one a fundamental reaction intermediate during aromatic chain reactions and has been the subject of a large number of spectroscopic studies. 3 Furthermore, the delocalized π systems of aromatic molecules have been extensively investigated to explain substitution effects. Schüler et al 4 first observed an emission line near 450 nm in the electronic spectrum of the benzyl radical.…”

Evidence of Molecular Rearrangement in Benzyl-type Radicals

“…The hyperfine coupling constant depends on the symmetry of molecules, the kind of substituents, and position of substitution. Table 2 shows the comparison of calculated results f Bond dissociation energy (kcal/mol) of C-H bond calculated from equation (1). for difluorobenzyl radical isomers, in which 3,5-isomer exhibits the least stability among isomers.…”

“…[1][2][3] With the knowledge based on the electronic structure of the benzyl radical, the effect of substitution on the electronic energy of benzyl-type radicals has been extensively examined to understand the substitution effect.…”

Vibronic Emission Spectra of Jet-Cooled o-Cyanobenzyl Radical

“…Of many benzyl-type radicals, the assignments of vibronic bands of xylyl radicals have been extensively carried out to determine the vibrational mode frequencies in the ground electronic state. 4,5 The torsional contribution of the methyl rotor has been obtained from simulation of the rotational contours of the high resolution Fourier transform emission spectra. 6 As for halogen-substituted benzyl-type radicals, many vibrational modes of fluorobenzyl radicals in the ground electronic state have been determined using different spectroscopic techniques.…”