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Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

J. Chem. Phys. 129, 084301 (2008); doi:10.1063/1.2966004

Published 22 August 2008

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Benjamin L. FitzPatrick,1 Kai-Chung Lau,1 Laurie J. Butler,1 Shih-Huang Lee,2 and Jim Jr-Min Lin3
1The James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA
2National Synchrotron Radiation Research Center, Hsinchu, 30076 Taiwan, Republic of China
3Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, 10617 Taiwan, Republic of China
These experiments study the preparation of and product channels resulting from OCH2CHCH2, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3  nm produces chlorine atoms and c-OCH2CHCH2 radicals; these undergo a facile ring opening to the OCH2CHCH2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8  eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33  kcal/mol. To elucidate the product channels resulting from the OCH2CHCH2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C3H4O  (acrolein)+H, C2H4+HCO (formyl radical), and H2CO (formaldehyde)+C2H3. A small signal from C2H2O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C2H5+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to each of these product channels calculated at the CCSD(T)/aug-cc-pVQZ level of theory, although a clean determination of the barrier energy to H+acrolein is precluded by the substantial partitioning into rotational energy during the photolytic production of the nascent radicals. We compare the measured branching fraction to the H+acrolein product channel with a statistical prediction based on the calculated transition states. ©2008 American Institute of Physics
History: Received 25 April 2008; accepted 9 July 2008; published 22 August 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/084301/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Cf
    Atom and radical chemical reactions; chain reactions, molecule-molecule reactions
  • 82.50.Hp
    Chemical processes caused by visible and UV light
  • 33.80.Rv
    Multiphoton ionization and excitation to highly excited states in molecules
  • YEAR: 2008

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (49)
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  1. C. S. McEnally, L. D. Pfefferle, B. Atakan, and K. Kohse-Hoinghaus, Prog. Energy Combust. Sci. 32, 247 (2006).
  2. J. W. Bozzelli and A. M. Dean, J. Phys. Chem. 97, 4427 (1993).
  3. J. Lee and J. W. Bozzelli, Proc. Combust. Inst. 30, 1015 (2005).
  4. R. P. Ruiz, K. D. Bayes, M. T. Macpherson, and M. J. Pilling, J. Phys. Chem. 85, 1622 (1981).
  5. N. M. Marinov, M. J. Castaldi, C. F. Melius, and W. Tsang, Combust. Sci. Technol. 128, 295 (1997).
  6. N. M. Marinov, W. J. Pitz, C. K. Westbrook, A. M. Vincitore, M. J. Castaldi, S. M. Senkan, and C. F. Melius, Combust. Flame 114, 192 (1998).
  7. C. S. McEnally and L. D. Pfefferle, Combust. Flame 143, 246 (2005).
  8. I. R. Slagle, J. R. Bernhardt, D. Gutman, M. A. Hanning-Lee, and M. J. Pilling, J. Phys. Chem. 94, 3652 (1990).
  9. H.-C. Kwon, J.-H. Park, H. Lee, H.-K. Kim, Y.-S. Choi, and J.-H. Choi, J. Chem. Phys. 116, 2675 (2002).
  10. J.-H. Park, H. Lee, H.-C. Kwon, H.-K. Kim, Y.-S. Choi, and J.-H. Choi, J. Chem. Phys. 117, 2017 (2002).
  11. S.-K. Park, L.-K. Kwon, H. Lee, and J.-H. Choi, J. Chem. Phys. 120, 7976 (2004).
  12. J.-H. Choi, Int. Rev. Phys. Chem. 25, 613 (2006).
  13. J.-H. Park, H. Lee, and J.-H. Choi, J. Chem. Phys. 119, 8966 (2003).
  14. N. Balucani and P. Casavecchia, AIP Conf. Proc. CP855, 17 (2006).
  15. F. Leonori, N. Balucani, G. Capozza, E. Segoloni, D. Stranges, and P. Casavecchia, Phys. Chem. Chem. Phys. 9, 1307 (2007).
  16. L. J. Butler and D. M. Neumark, J. Phys. Chem. 100, 12801 (1996).
  17. C. C. Wang, Y. T. Lee, J. J. Lin, J. Shu, Y. Y. Lee, and X. J. Yang, J. Chem. Phys. 117, 153 (2002).
  18. S.-H. Lee, Y.-Y. Lee, Y. T. Lee, and X. Yang, J. Chem. Phys. 119, 827 (2003).
  19. J. J. Lin, Y. Chen, Y. Y. Lee, Y. T. Lee, and X. Yang, Chem. Phys. Lett. 361, 374 (2002).
  20. X. Yang, J. Lin, Y. T. Lee, D. A. Blank, A. G. Suits, and A. M. Wodtke, Rev. Sci. Instrum. 68, 3317 (1997).
  21. Y. T. Lee, J. D. McDonald, P. R. LeBreton, and D. R. Herschbach, Rev. Sci. Instrum. 40, 1402 (1969).
  22. B. L. FitzPatrick, M. Maienschein-Cline, L. J. Butler, S.-H. Lee, and J. J. Lin, J. Phys. Chem. A 111, 12417 (2007).
  23. N. R. Daly, Rev. Sci. Instrum. 31, 264 (1960).
  24. A. J. R. Heck and D. W. Chandler, Annu. Rev. Phys. Chem. 46, 335 (1995).
  25. A. T. J. B. Eppink and D. H. Parker, Rev. Sci. Instrum. 68, 3477 (1997).
  26. Y. Sato, Y. Matsumi, M. Kawasaki, K. Tsukiyama, and R. Bersohn, J. Phys. Chem. 99, 16307 (1995).
  27. K. C. Lau, Y. Liu, and L. J. Butler, J. Chem. Phys. 123, 054322 (2005).
  28. Y. Liu and L. J. Butler, J. Chem. Phys. 121, 11016 (2004).
  29. Y. Liu, K. C. Lau, and L. J. Butler, J. Phys. Chem. A 110, 5379 (2006).
  30. V. Dribinski, A. Ossadtchi, V. A. Mandelshtam, and H. Reisler, Rev. Sci. Instrum. 73, 2634 (2002).
  31. A. G. Baboul, L. A. Curtiss, P. C. Redfern, and K. Raghavachari, J. Chem. Phys. 110, 7650 (1999).
  32. L. A. Curtiss, P. C. Redfern, V. Rassolov, G. Kedziora, and J. A. Pople, J. Chem. Phys. 114, 9287 (2001).
  33. M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN03, Revision C.02, Gaussian, Inc., Pittsburgh, PA, 2003.
  34. MOLPRO, version 2006.1, a package of ab initio programs, designed by H.-J. Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schütz et al. (see http://www.molpro.net).
  35. P. J. Knowles, C. Hampel, and H.-J. Werner, J. Chem. Phys. 99, 5219 (1993);
    36. 112, 3106E (2000).
  36. See EPAPS Document No. E-JCPSA6-129-603832 for structures, energies (without zero point correction), unscaled vibrational frequencies, and moments of inertia of the intermediates and transition states calculated for the O+allyl reaction at the RCCSD(T)/aug-cc-pVQZ||UCCSD/aug-cc-pVDZ level of theory. For more information on EPAPS, see http://www.aip.org/pubservs/epaps.html. [EPAPS]
  37. B. L. FitzPatrick, L. J. Butler, S.-H. Lee, and J. J. Lin (in preparation).
  38. P. M. Guyon, W. A. Chupka, and J. Berkowitz, J. Chem. Phys. 65, 1419 (1976).
  39. B. Ruscic, personal communication, September 2007. These are unpublished interim results from the Active Thermochemical Tables (ATcT) ver. 1.36 and the Core (Argonne) Thermochemical Network, ver. 1.064.
  40. J. Wang, L. Wei, B. Yang et al., Chem. Res. Chin. Univ. 22, 375 (2006).
  41. J. C. Person and P. P. Nicole, J. Chem. Phys. 49, 5421 (1968).
  42. T. A. Cool, J. Wang, K. Nakajima, C. A. Taatjes, and A. Mcllroy, Int. J. Mass. Spectrom. 247, 18 (2005).
  43. F. A. Grimm, T. A. Whitley, P. R. Keller, and J. W. Taylor, Chem. Phys. 154, 303 (1991).
  44. J. C. Robinson, N. E. Sveum, and D. I. M. Neumark, J. Chem. Phys. 119, 5311 (2003).
  45. R. Liyanage, T.-A. Yang, S. Hashimoto, R. J. Gordon, and R. W. Field, J. Chem. Phys. 103, 6811 (1995).
  46. The RRKM code is obtained from W. L. Hase and D. L. Bunker, Quantum Chemistry Program Exchange 234 (1974). To calculate the sums and densities of states, we used the Whitten Rabinovitch semiclassical technique implemented in that software.
  47. M. J. Bell, K.-C. Lau, M. J. Krisch, D. I. G. Bennett, L. J. Butler, and F. Weinhold, J. Phys. Chem. A 111, 1762 (2007).
  48. L. R. McCunn, M. J. Krisch, K. Takematsu, L. J. Butler, and J. Shu, J. Phys. Chem. A 108, 7889 (2004).
  49. D. E. Szpunar, J. L. Miller, L. J. Butler, and F. Qi, J. Chem. Phys. 120, 4223 (2004).

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