Time- and frequency-resolved photoionisation of the allyl radical

Schultz, Thomas; Clarke, James Stanier; Gilbert, Thomas M.; Deyerl, Hans-Jürgen; Fischer, Ingo

doi:10.1039/a909276e

Cited by 34 publications

(52 citation statements)

References 53 publications

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“…69 Fischer, Schultz, and co-workers used picosecond TRPES to measure lifetimes of vibrational levels of the B, C, and D excited electronic states of the allyl radical, all of which lie about 5 eV above the ground state. [70][71][72] The first experiments at femtosecond time resolution incorporating electron detection were reported in the mid-1990s. In 1993, Baumert, Gerber and coworkers, 73 followed by Stolow and co-workers in 1995, 33,34 applied femtosecond time-resolved ZEKE spectroscopy to vibrational wave packet dynamics in Na 3 and I 2 , respectively.…”

Section: Time-resolved Photoelectron Spectroscopy Experimentsmentioning

confidence: 99%

Femtosecond Time-Resolved Photoelectron Spectroscopy

2004

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Section: Time-resolved Photoelectron Spectroscopy Experimentsmentioning

confidence: 99%

Femtosecond Time-Resolved Photoelectron Spectroscopy

2004

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“…This was demonstrated for the allyl radical ͑C 3 H 5 ͒, where time-resolved photoelectron spectroscopy showed that the electronically excited radicals return to the ground state surface within 20 ps or less by internal conversion in a two-step process. 8,9 Allyl subsequently dissociates, preferentially to allene+ H, following a mechanism appropriately modeled by statistical reaction theories. 10 In alkyl radicals on the other hand it is questionable whether purely statistical models can explain the observed dissociation rates: An investigation of the hydrogen atom loss from ethyl radical ͑C 2 H 5 ͒ upon excitation into the 2 2 AЈ state, nominally the 3s Rydberg state, yielded a rate constant more than four orders of magnitude slower than expected from simple RRKM calculations.…”

Section: Introductionmentioning

confidence: 99%

Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: Ethyl, propargyl, and benzyl

Zierhut

Noller

Schultz

et al. 2005

The Journal of Chemical Physics

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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 decay with a time constant 50± 10 fs was determined. The 4 2 B 2 state of benzyl excited at 255 nm decays within 150± 30 fs.

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“…[1][2][3][4][5][6][7] The work presented here uses a technique developed to study the unimolecular dissociation channels of isomerically selected radicals 8 in continuation of a previous study in which allyl iodide was used as a photolytic precursor of the allyl radical. 7 Unlike the other prior studies on allyl radicals, these studies examine the dissociation dynamics of highly rotationally excited allyl radicals.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation of allyl-d2 iodide excited at 193 nm: Stability of highly rotationally excited H2CDCH2 radicals to C–D fission

Szpunar

Liu

McCullagh

et al. 2003

The Journal of Chemical Physics

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The photodissociation of allyl-d 2 iodide (H 2 CϭCDCH 2 I) and the dynamics of the nascent allyl-d 2 radical (H 2 CCDCH 2 ) were studied using photofragment translational spectroscopy. A previous study found the allyl radical stable at internal energies up to 15 kcal/mol higher than the 60 kcal/mol barrier to alleneϩH formation as the result of a centrifugal barrier. The deuterated allyl radical should then also show a stability to secondary dissociation at internal energies well above the barrier due to centrifugal effects. A comparison in this paper shows the allyl-d 2 radical is stable to alleneϩD formation at energies of 2-3 kcal/mol higher than that of the nondeuterated allyl radical following photolysis of allyl iodide at 193 nm. This is most likely a result of a combination of the slight raising of the barrier from the difference in zero-point levels and a reduction of the impact parameter of the dissociative fragments due to the decrease in frequency of the C-D bending modes, and therefore alleneϩD product orbital angular momentum, ͉L ជ ͉ϭ͉v ជ rel ͉b. The integrated signal taken at m/eϭ40 ͑allene͒ and m/eϭ41 (allene-d 1 and propyne-d 3 ) shows a minor fraction of the allyl-d 2 radicals isomerize to the 2-propenyl radical, in qualitative support of earlier conclusions of the domination of direct alleneϩH formation over isomerization.

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Time- and frequency-resolved photoionisation of the allyl radical

Cited by 34 publications

References 53 publications

Femtosecond Time-Resolved Photoelectron Spectroscopy

Femtosecond Time-Resolved Photoelectron Spectroscopy

Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: Ethyl, propargyl, and benzyl

Photodissociation of allyl-d2 iodide excited at 193 nm: Stability of highly rotationally excited H2CDCH2 radicals to C–D fission

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