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Dissociation dynamics of the methylsulfonyl radical and its photolytic precursor CH3SO2Cl
The dissociation dynamics of methylsulfonyl radicals generated from the photodissociation of CH3SO2Cl at 193 nm is investigated by measuring product velocities in a crossed laser-molecular beam scatte...

Determining the CH3SO2-->CH3+SO2 barrier from methylsulfonyl chloride photodissociation at 193 nm using velocity map imaging

J. Chem. Phys. 131, 044304 (2009); doi:10.1063/1.3159556

Published 22 July 2009

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Britni J. Ratliff,1 Xiaonan Tang,1 Laurie J. Butler,1 David E. Szpunar,2 and Kai-Chung Lau3
1Department of Chemistry and The James Franck Institute, University of Chicago, Chicago, Illinois 60637, USA
2Department of Biological, Chemical, and Physical Sciences, Roosevelt University, Schaumburg, Illinois 60173, USA
3Department of Biology and Chemistry, City University of Hong Kong, Hong Kong
These imaging experiments study the formation of the methylsulfonyl radical, CH3SO2, from the photodissociation of CH3SO2Cl at 193 nm and determine the energetic barrier for the radical's subsequent dissociation to CH3+SO2. We first state-selectively detect the angular and recoil velocity distributions of the Cl(2P3/2) and Cl(2P1/2) atoms to further refine the distribution of internal energy partitioned to the momentum-matched CH3SO2 radicals. The internal energy distribution of the radicals is bimodal, indicating that CH3SO2 is formed in both the ground state and low-lying excited electronic states. All electronically excited CH3SO2 radicals dissociate, while those formed in the ground electronic state have an internal energy distribution which spans the dissociation barrier to CH3+SO2. We detect the recoil velocities of the energetically stable methylsulfonyl radicals with 118 nm photoionization. Comparison of the total recoil translational energy distribution for all radicals to the distribution obtained from the detection of stable radicals yields an onset for dissociation at a translational energy of 70±2  kcal/mol. This onset allows us to derive a CH3SO2-->CH3+SO2 barrier height of 14±2  kcal/mol; this determination relies on the S–Cl bond dissociation energy, taken here as the CCSD(T) predicted energy of 65.6 kcal/mol. With 118 nm photoionization, we also detect the velocity distribution of the CH3 radicals produced in this experiment. Using the velocity distributions of the SO2 products from the dissociation of CH3SO2 to CH3+SO2 presented in the following paper, we show that our fastest detected methyl radicals are not from these radical dissociation channels, but rather from a primary S–CH3 bond photofission channel in CH3SO2Cl. We also present critical points on the ground state potential energy surface of CH3SO2 at the //CCSD(T)/aug-cc-pV(Q+d)ZCCSD(T)/6-311++G(2df,p) level. We include harmonic zero-point vibrational corrections as well as core-valence and scalar-relativistic corrections. The CCSD(T) predicted barrier of 14.6 kcal/mol for CH3SO2-->CH3+SO2 agrees well with our experimental measurement. These results allow us to predict the unimolecular dissociation kinetics of CH3SO2 radicals and critique the analysis of prior time-resolved photoionization studies on this system. ©2009 American Institute of Physics
History: Received 20 February 2009; accepted 4 June 2009; published 22 July 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/044304/1
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EDITORIALLY RELATED

  1. Dissociation dynamics of the methylsulfonyl radical and its photolytic precursor CH3SO2Cl
    Bridget W. Alligood et al.
    J. Chem. Phys. 131, 044305 (2009)

Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 82.50.Hp
    Chemical processes caused by visible and UV light
  • 82.30.Cf
    Atom and radical chemical reactions; chain reactions, molecule-molecule reactions
  • 82.20.Kh
    Potential energy surfaces for chemical reactions
  • 82.80.Gk
    Chemical analytical methods involving vibrational spectroscopy
  • YEAR: 2009

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (37)
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  1. S. B. Barone, A. A. Turnipseed, and A. R. Ravishankara, Faraday Discuss. 100, 39 (1995).
  2. K. –C. Lau, Y. Liu, and L. J. Butler, J. Chem. Phys. 123, 054322 (2005).
  3. X. N. Tang, B. J. Ratliff, B. L. FitzPatrick, and L. J. Butler, J. Phys. Chem. B 112, 16058 (2008).
  4. L. Zhu and J. W. Bozzelli, J. Mol. Struct.: THEOCHEM 728, 147 (2005).
  5. J. M. L. Martin, J. Chem. Phys. 108, 2791 (1998).
  6. J. M. L. Martin, Chem. Phys. Lett. 310, 271 (1999).
  7. T. H. Dunning, Jr., K. A. Peterson, and A. K. Wilson, J. Chem. Phys. 114, 9244 (2001).
  8. A. K. Wilson and T. H. Dunning, Jr., J. Chem. Phys. 119, 11712 (2003).
  9. A. K. Wilson and T. H. Dunning, Jr., J. Phys. Chem. A 108, 3129 (2004).
  10. R. D. Bell and A. K. Wilson, Chem. Phys. Lett. 394, 105 (2004).
  11. N. X. Wang and A. K. Wilson, J. Phys. Chem. A 109, 7187 (2005).
  12. D. Borissenko, A. Kukui, G. Laverdet, and G. Le Bras, J. Phys. Chem. A 107, 1155 (2003).
  13. A. Kukui, V. Bossoutrot, G. Laverdet, and G. Le Bras, J. Phys. Chem. A 104, 935 (2000).
  14. A. Ray, I. Vassalli, G. Laverdet, and G. Le Bras, J. Phys. Chem. 100, 8895 (1996) and earlier references within.
  15. A. J. Frank and F. Turecek, J. Phys. Chem. A 103, 5348 (1999).
  16. J. C. Owrutsky, H. H. Nelson, and A. P. Baronavski, J. Phys. Chem. A 105, 1440 (2001).
  17. B. W. Alligood, B. L. FitzPatrick, E. J. Glassman, L. J. Butler, and K.-C. Lau, J. Chem. Phys. 131, 044305 (2009).
  18. A. J. R. Heck and D. W. Chandler, Annu. Rev. Phys. Chem. 46, 335 (1995).
  19. A. T. J. B. Eppink and D. H. Parker, Rev. Sci. Instrum. 68, 3477 (1997).
  20. Y. Sato, Y. Matsumi, M. Kawasaki, K. Tsukiyama, and R. Bersohn, J. Phys. Chem. 99, 16307 (1995).
  21. Y. Liu and L. J. Butler, J. Chem. Phys. 121, 11016 (2004).
  22. Note that most authors label the upper state for detection of Cl(2P1/2) as the 4p 2P1/2 state from C. E. Moore, NSRDS-NBS 35, 1 (1971)
    23. however, the NIST Atomic Spectra Database has adopted the reassignment of this upper state at 85 917.937  cm−1 to a 2S state, as recommended in the comprehensive reanalysis of the chlorine spectrum by L. J. Radziemski, Jr. and V. Kaufman, J. Opt. Soc. Am. 59, 424 (1969). (To avoid confusion, we give the original C. E. Moore assignment here. For the energy of the transition, we use the NIST value of 85 917.937–882.3515  cm−1.)
  23. B. Chang, R. C. Hoetzlein, J. A. Mueller, J. D. Geiser, and P. L. Houston, Rev. Sci. Instrum. 69, 1665 (1998).
  24. C. Hampel, K. A. Peterson, and H. Werner, Chem. Phys. Lett. 190, 1 (1992)
    25. M. J. O. Deegan and P. J. Knowles, ibid. 227, 321 (1994)
    P. J. Knowles, C. Hampel, and H. J. Werner, J. Chem. Phys. 99, 5219 (1993).
  25. T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989).
  26. K. A. Peterson and T. H. Dunning, Jr., J. Chem. Phys. 117, 10548 (2002).
  27. W. A. de Jong, R. J. Harrison, and D. A. Dixon, J. Chem. Phys. 114, 48 (2001)
    28. M. Douglas and N. M. Kroll, Ann. Phys. 82, 89 (1974).
  28. H. -J. Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schütz, P. Celani, T. Korona, G. Rauhut, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, C. Hampel, G. Hetzer, A. W. Lloyd, S. J. McNicholas, W. Meyer, M. E. Mura, A. Nicklaß, P. Palmieri, R. Pitzer, U. Schumann, H. Stoll, A. J. Stone, R. Tarroni, and T. Thorsteinsson, MOLPRO is a package of ab initio programs.
  29. C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. (U.S.) Circ. No. 467 (U.S. GPO, Washingtons, D.C., 1949).
  30. See EPAPS supplementary material at http://dx.doi.org/10.1063/1.3159556 for energies, geometries, and rotational constants of the intermediates and transition states for the CH3SO2 potential energy surface calculated at the CCSD(T) level of theory. Also found in the supplementary material are some experimental data and rate constant calculations not included in the manuscript. [EPAPS]
  31. M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 03, Revision E.01, Gaussian, Inc., Wallingford CT, 2004.
  32. V. Dribinski, A. Ossadtchi, V. A. Mandelshtam, and H. Reisler, Rev. Sci. Instrum. 73, 2634 (2002).
  33. R. Liyanage, Y. A. Yang, S. Hashimoto, R. J. Gordon, and R. W. Field, J. Chem. Phys. 103, 6811 (1995).
  34. J. Berkowitz, G. B. Ellison, and D. Gutman, J. Phys. Chem. 98, 2744 (1994).
  35. T. Shibata, H. Li, H. Katayanagi, and T. Suzuki, J. Phys. Chem. A 102, 3643 (1998).
  36. MULTIWELL-2009.2 software, May 2009, designed and maintained by J. R. Barker with contributors N. F. Ortiz, J. M. Preses, L. L. Lohr, A. Maranzana, P. J. Stimac, and L. T. Nguyen, University of Michigan, Ann Arbor, MI, http://aoss.engin.umich.edu/multiwell/
    37. J. R. Barker, Int. J. Chem. Kinet. 33, 232 (2001).
  37. See Eq. 3.21 in K. A. Holbrook, M. J. Pilling, and S. H. Robertson, Unimolecular Reactions, 2nd ed. (Wiley, Chichester, 1996).

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