The nonradiative decay of the allyl radical excited B 2A1 state studied by picosecond time-resolved photoelectron spectroscopy

Schultz, Thomas; Fischer, Ingo

doi:10.1063/1.475121

Cited by 36 publications

(40 citation statements)

References 41 publications

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“…On the one hand, we applied picosecond time-resolved photoelectron spectroscopy to follow the initial decay of low-lying vibrational levels of the B-state in real time, 20 obtaining lifetimes around 20 ps due to internal conversion of the B-state. In a different experiment we detected the loss of hydrogen atoms from allyl radicals upon UV excitation 21 by time-resolved ionization of H-atoms with Lyman-␣ radiation with a rate of 4 ϫ10 7 s Ϫ1 , i.e., on a ns time scale.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of the allyl radical: The lifetimes of the ultraviolet bands

Schultz¹,

Fischer²

1998

The Journal of Chemical Physics

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Articles you may be interested in Gas-phase photodissociation of CH3COCN at 308 nm by time-resolved Fourier-transform infrared emission spectroscopy J. Chem. Phys. 136, 044302 (2012) We report ͓1ϩ1Ј͔ picosecond time-resolved pump-probe photoelectron spectra of the UV bands of the allyl radical. The experiments are performed in a molecular beam of allyl radicals, generated by supersonic jet flash pyrolysis. Photoelectron spectroscopy in a magnetic bottle is shown to be a suitable method for investigating the photophysics of organic radicals. Lifetimes were obtained for all vibronic bands between 250 and 238 nm previously assigned by MPI spectroscopy to the electronically excited B 2 A 1 , C 2 B 1 , and D 2 B 2 states, with values ranging from 20 ps to 9 ps. The nonradiative decay is due to internal conversion to the electronic ground state. Information on the structure of the allyl cation is deduced from the photoelectron spectrum.

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Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of the allyl radical: The lifetimes of the ultraviolet bands

Schultz¹,

Fischer²

1998

The Journal of Chemical Physics

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“…However, because of the difficulty in producing these transient species, often limited information is available under well-defined experimental conditions. Theoretical studies on the reaction of hydrocarbon radicals are also quite scarce except for some calculations on a few simple systems, among which the reactions of allyl radical (C 3 H 5 •) [18][19][20][21][22][23][24] and ethane radical (C 2 H 5 •) [25][26][27][28][29][30][31][32][33][34][35][36] have attracted more attentions than others. Estupiñán et al studied the reactions of C 2 H 5 , n-C 3 H 7 , and i-C 3 H 7 radicals with O 2 using the technique of laser photolysis/long-path frequency-modulation spectroscopy and ab initio method [37].…”

Section: Introductionmentioning

confidence: 99%

A theoretical study on the reaction mechanism of O2 with C4H9• radical

Gong

2011

J Mol Model

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Ab initio calculations have been performed using the complete basis set model (CBS-QB3) to study the reaction mechanism of butane radical (C(4)H(9)•) with oxygen (O(2)). On the calculated potential energy surface, the addition of O(2) to C(4)H(9)• forms three intermediates barrierlessly, which can undergo subsequent isomerization or decomposition reaction leading to various products: HOO• + C(4)H(8), C(2)H(5)• + CH(2)CHOOH, OH• + C(3)H(7)CHO, OH• + cycle-C(4)H(8)O, CH(3)• + CH(3)CHCHOOH, CH(2)OOH• + C(3)H(6). Five pathways are supposed in this study. After taking into account the reaction barrier and enthalpy, the most possible reaction pathway is C(4)H(9)• + O(2) → IM1 → TS5 → IM3 → TS6 → IM4 → TS7 → OH• + cycle-C(4)H(8)O.

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“…Fischer et al have applied a time-resolved photoelectron spectroscopy to study photodissociation kinetics and dynamics of several hydrocarbon radicals, such as allyl (C 3 H 5 ), propargyl (C 3 H 3 ), and ethyl (C 2 H 5 ) produced by the supersonic flash pyrolysis source. [2][3][4][5][6][7][8] Barney Ellison et al studied the pyrolysis of alkyl nitrite ͑RONO͒ to obtain infrared spectra and the number density of radicals of about 10 14 /cm 3 . 9 In recent years, Choi and co-workers conducted laser induced fluorescence ͑LIF͒ spectroscopic investigations to characterize internal state distributions of nitric oxide and a͒ Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH

Park

Lee

Kwon

et al. 2002

The Journal of Chemical Physics

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The reaction dynamics of ground-state atomic oxygen ͓O( 3 P)͔ with allyl radicals (C 3 H 5 ) has been investigated by applying a combination of crossed beams and laser induced fluorescence techniques. The reactants O( 3 P) and C 3 H 5 were produced by the photodissociation of NO 2 and the supersonic flash pyrolysis of precursor allyl iodide, respectively. A new exothermic channel of O( 3 P) ϩC 3 H 5 →C 3 H 4 ϩOH was observed and the nascent internal state distributions of the product OH (X 2 ⌸:Љϭ0,1) showed substantial bimodal internal excitations of the low-and high-NЉ components without ⌳-doublet and spin-orbit propensities in the ground and first excited vibrational states. With the aid of the CBS-QB3 level of ab initio theory and Rice-Ramsperger-Kassel-Marcus calculations, it is predicted that on the lowest doublet potential energy surface the major reaction channel of O( 3 P) with C 3 H 5 is the formation of acrolein (CH 2 CHCHO)ϩH, which is consistent with the previous bulk kinetic experiments performed by Gutman et al. ͓J. Phys. Chem. 94, 3652 ͑1990͔͒. The counterpart C 3 H 4 of the probed OH product in the title reaction is calculated to be allene after taking into account the factors of reaction enthalpy, barrier height and the number of intermediates involved along the reaction pathway. On the basis of population analyses and comparison with prior calculations, the statistical picture is not suitable to describe the reactive atom-radical scattering processes, and the dynamics of the title reaction is believed to proceed through two competing dynamical pathways. The major low NЉ-components with significant vibrational excitation may be described by the direct abstraction process, while the minor but extraordinarily hot rotational distribution of high NЉ-components implies that some fraction of reactants is sampled to proceed through the indirect short-lived addition-complex forming process.

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The nonradiative decay of the allyl radical excited B 2A1 state studied by picosecond time-resolved photoelectron spectroscopy

Cited by 36 publications

References 41 publications

Time-resolved photoelectron spectroscopy of the allyl radical: The lifetimes of the ultraviolet bands

Time-resolved photoelectron spectroscopy of the allyl radical: The lifetimes of the ultraviolet bands

A theoretical study on the reaction mechanism of O2 with C4H9• radical

Atom-radical reaction dynamics of O(3P)+C3H5→C3H4+OH: Nascent rovibrational state distributions of product OH

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