2005
DOI: 10.1063/1.1857475
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Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: Ethyl, propargyl, and benzyl

Abstract: The excited state decay of the hydrocarbon radicals ethyl, C 2 H 5 ; propargyl, C 3 H 3 ; and benzyl, C 7 H 7 was investigated by femtosecond time-resolved photoionization. Radicals were generated by flash pyrolysis of n-propyl nitrite, propargyl bromide, and toluene, respectively. It is shown that the 2 2 AЈ ͑3s͒ Rydberg state of ethyl excited at 250 nm decays with a time constant of 20 fs. No residual signal was observed at longer delay times. For the 3 2 B 1 state of propargyl excited at 255 nm a slower dec… Show more

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Cited by 37 publications
(35 citation statements)
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“…33,34 The excited 3s Rydberg state decays via a conical intersection in a nonclassical H-bridged geometry, producing a fast and anisotropic channel with direct H-atom scission via the nonclassical H-bridged transition state and a slow and isotropic channel from unimolecular dissociation of the hot radical after internal conversion. 33,36,37 Site-selective loss of the β hydrogen atom is confirmed by using the partially deuterated CH 3 CD 2 radical. 33 Photodissociation of the jet-cooled propyl radicals was investigated by Hatom photofragment Doppler spectroscopy.…”
Section: Introductionmentioning
confidence: 88%
“…33,34 The excited 3s Rydberg state decays via a conical intersection in a nonclassical H-bridged geometry, producing a fast and anisotropic channel with direct H-atom scission via the nonclassical H-bridged transition state and a slow and isotropic channel from unimolecular dissociation of the hot radical after internal conversion. 33,36,37 Site-selective loss of the β hydrogen atom is confirmed by using the partially deuterated CH 3 CD 2 radical. 33 Photodissociation of the jet-cooled propyl radicals was investigated by Hatom photofragment Doppler spectroscopy.…”
Section: Introductionmentioning
confidence: 88%
“…They were assigned to excitation into the 3s, 3p, and 3d states. 11,12 In femtosecond time-resolved experiments, short excited-state lifetimes were found for ethyl, 13 t-butyl, 14 and the hexyl-isomer dimethylbutyl 15 and explained by a rapid internal conversion (IC) to the ground state. The most important unimolecular reaction channel in many radicals is the loss of a hydrogen atom and formation of a closed shell molecule.…”
Section: Introductionmentioning
confidence: 99%
“…This is common in time-resolved spectra after IC to the ground state, because the Franck-Condon factors between the vibrationally excited ground-state levels and low ionic states are generally poor. In our earlier work on the D 2 B 2 state 8 we observed a time constant of 150 fs for deactivation at 255 nm. A residual signal was also present, but the scan lengths and the signalto-noise ratio were insufficient to determine a second time constant or deduce information on the final state.…”
Section: Time-resolved Tracesmentioning
confidence: 99%
“…Time-resolved pump-probe spectroscopy with short laser pulses allows the direct observation of the primary photophysical processes 5,6 and can address this issue. We demonstrated this approach in the past for a number of hydrocarbon radicals, [7][8][9] as well as for carbenes. 10,11 Benzyl is an aromatic radical that is stabilized by a delocalized -system.…”
Section: Introductionmentioning
confidence: 99%
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