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Title: The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.

Abstract

The photodissociation of allyl iodide (C{sub 3}H{sub 5}I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*({sup 2}P{sub 1/2}) is more important than previously suspected.

Authors:
; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
939881
Report Number(s):
ANL/CHM/JA-57078
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US200823%%436
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 124; Journal Issue: 2006
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALLYL RADICALS; STABILITY; PHOTOLYSIS; IODINE COMPOUNDS; DISSOCIATION; CHEMICAL BONDS; CLEAVAGE; ROTATIONAL STATES; VIBRATIONAL STATES; CHEMICAL REACTION KINETICS

Citation Formats

Fan, H., Pratt, S. T., and Chemistry. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.. United States: N. p., 2006. Web. doi:10.1063/1.2352733.
Fan, H., Pratt, S. T., & Chemistry. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.. United States. doi:10.1063/1.2352733.
Fan, H., Pratt, S. T., and Chemistry. Sun . "The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.". United States. doi:10.1063/1.2352733.
@article{osti_939881,
title = {The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.},
author = {Fan, H. and Pratt, S. T. and Chemistry},
abstractNote = {The photodissociation of allyl iodide (C{sub 3}H{sub 5}I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*({sup 2}P{sub 1/2}) is more important than previously suspected.},
doi = {10.1063/1.2352733},
journal = {J. Chem. Phys.},
number = 2006,
volume = 124,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
  • The photodissociation of allyl-d2 iodide (H2C=CDCH2I) and the dynamics of the nascent allyl-d2 radical (H2CCDCH2) 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 allene + H 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-d2 radical is stable to allene + D formation at energies of 2-3 kcal/mol highermore » than that of the non-deuterated 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 the refore allene + D product orbital angular momentum. Integrated signal taken at m/e = 40 (allene) and m/e = 41 (allene-d1 and propyne-d3) shows a minor fraction of the allyl-d2 radicals isomerize to the 2-propenyl radical, in qualitative support of earlier conclusions of the domination of direct allene + H formation over isomerization.« less
  • The photodissociation of perdeuterated propargyl (D{sub 2}CCCD) and propynyl (D{sub 3}CCC) radicals was investigated using fast beam photofragment translational spectroscopy. Radicals were produced from their respective anions by photodetachment at 540 nm and 450 nm (below and above the electron affinity of propynyl). The radicals were then photodissociated by 248 nm or 193 nm light. The recoiling photofragments were detected in coincidence with a time- and position-sensitive detector. Three channels were observed: D{sub 2} loss, CD + C{sub 2}D{sub 2}, and CD{sub 3} + C{sub 2}. Obervation of the D loss channel was incompatible with this experiment and was notmore » attempted. Our translational energy distributions for D{sub 2} loss peaked at nonzero translational energy, consistent with ground state dissociation over small (< 1 eV) exit barriers with respect to separated products. Translational energy distributions for the two heavy channels peaked near zero kinetic energy, indicating dissociation on the ground state in the absence of exit barriers.« less
  • A new measurement of the photodissociation of CH{sub 3}I at 193 nm is reported in which we use a combination of vacuum ultraviolet photoionization and velocity map ion imaging. The iodine photofragments are probed by single-photon ionization at photon energies above and below the photoionization threshold of I({sup 2}P{sub 3/2}). The relative I({sup 2}P{sub 3/2}) and I{sup *}({sup 2}P{sub 1/2}) photoionization cross sections are determined at these wavelengths by using the known branching fractions for the photodissociation at 266 nm. Velocity map ion images indicate that the branching fraction for I({sup 2}P{sub 3/2}) atoms is non-zero, and yield a valuemore » of 0.07 ┬▒ 0.01. Interestingly, the translational energy distribution extracted from the image shows that the translational energy of the I({sup 2}P{sub 3/2}) fragments is significantly smaller than that of the I{sup *}({sup 2}P{sub 1/2}) atoms. This observation indicates the internal rotational/vibrational energy of the CH{sub 3} co-fragment is very high in the I({sup 2}P{sub 3/2}) channel. The results can be interpreted in a manner consistent with the previous measurements, and provide a more complete picture of the dissociation dynamics of this prototypical molecule.« less
  • No abstract prepared.
  • The photodissociation of perdeuterated propargyl (D{sub 2}CCCD) and propynyl (D{sub 3}CCC) radicals was investigated using fast beam photofragment translational spectroscopy. Radicals were produced from their respective anions by photodetachment at 540 and 450 nm (below and above the electron affinity of propynyl). The radicals were then photodissociated at 248 or 193 nm. The recoiling photofragments were detected in coincidence with a time- and position-sensitive detector. Three channels were observed: D{sub 2} loss, CD+C{sub 2}D{sub 2}, and CD{sub 3}+C{sub 2}. Observation of the D loss channel was incompatible with this experiment and was not attempted. Our translational energy distributions for D{submore » 2} loss peaked at nonzero translational energy, consistent with ground state dissociation over small (<1 eV) exit barriers with respect to separated products. Translational energy distributions for the two heavy channels peaked near zero kinetic energy, indicating dissociation on the ground state in the absence of exit barriers.« less