Excitation and emission spectra of jet-cooled naphthylmethyl radicals.

Gas phase excitation and emission spectra of three naphthylmethyl radical chromophores are presented. These resonance-stabilized species, 1-naphthylmethyl, 2-naphthylmethyl, and α-acenaphthenyl, each possessing an sp(2) carbon adjacent to a naphthalene moiety, are studied by resonant two-color two-photon ionization, laser induced fluorescence, and dispersed fluorescence spectroscopy. Identification of the radicals is made through a combination of dispersed fluorescence and density functional theory calculations.

Laser-induced fluorescence and dispersed fluorescence spectroscopy of jet-cooled 1-phenylpropargyl radical.

The D(1)((2)A("))-D(0)((2)A(")) electronic transition of the resonance-stabilized 1-phenylpropargyl radical, produced in a jet-cooled discharge of 3-phenyl-1-propyne, has been investigated in detail by laser-induced fluorescence excitation and dispersed single vibronic level fluorescence (SVLF) spectroscopy.The transition is dominated by the origin band at 21,007 cm(-1), with weaker Franck-Condon activity observed in a(') fundamentals and even overtones and combinations of a(") symmetry. Ab initio and density functional theory calculations of the D(0) and D(1) geometries and frequencies were performed to support and guide the experimental assignments throughout.