Time- and frequency-resolved photoionization of the C (2)A(2) state of the benzyl radical, C(7)H(7).
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The Journal of chemical physics, ISSN: 1089-7690, Vol: 133, Issue: 7, Page: 074304
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- Physics and Astronomy; Chemistry; Benzyl radicals; Biexponential decay; Electronic ground state; Excitation wavelength; Femtosecond pumps; Flash pyrolysis; Free jets; Internal conversions; Multiphoton ionization spectra; Structure and dynamics; Vibronic bands; Wavelength ranges
The structure and dynamics of the C (2)A(2) electronically excited state of the benzyl radical, C(7)H(7), were investigated by nanosecond and femtosecond pump-probe photoionization. A free jet of benzyl radicals was generated by flash pyrolysis from the precursors 2-phenylethyl nitrite and toluene. Nanosecond multiphoton ionization spectra show a number of vibronic bands that are excited in the wavelength range of 290-310 nm. At excitation wavelengths of 305, 301, and 298 nm, rapid biexponential decay of the excited states was observed. Lifetimes at the C-state origin (305 nm excitation) are 400 fs and 4.5 ps. The lifetimes decrease with increasing excitation energy. The dynamics can be understood within a two-step internal conversion to the electronic ground state.