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Observation of the “missing” polar OCS dimer
A new infrared band at 2069.3  cm−1 is observed and assigned to the long-anticipated polar isomer of the OCS dimer, helping to explain apparent discrepancies among earlier studies. The...

Photodissociation of hydrogen halide molecules on free ice nanoparticles

J. Chem. Phys. 126, 071101 (2007); doi:10.1063/1.2709635

Published 15 February 2007

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Viktoriya Poterya and Michal Fárník
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague 8, Czech Republic

Petr Slavíček
Department of Physical Chemistry, Institute of Chemical Technology, Technická 5, Prague 6, Czech Republic

Udo Buck
Max-Planck Institut für Dynamik und Selbstorganization, Bunsenstrasse 10, D-37073 Göttingen, Germany

Vitaly V. Kresin
Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089-0484
Photodissociation of water clusters doped with HX(X=Br,Cl), molecules has been studied in a molecular beam experiment. The HX(H2O)n clusters are dissociated with 193  nm laser pulses, and the H fragments are ionized at 243.07  nm and their time-of-flight distributions are measured. Experiments with deuterated species DBr(H2O)n and HBr(D2O)n suggest that the photodissociation signal originates from the presence of the HX molecule on the water cluster, but does not come directly from a photolysis of the HX molecule. The H fragment is proposed to originate from the hydronium molecule H3O. Possible mechanisms of the H3O production are discussed. Experimental evidence suggests that acidic dissociation takes place in the cluster, but the H3O+ ion remains rather immobile. ©2007 American Institute of Physics
History: Received 10 January 2007; accepted 24 January 2007; published 15 February 2007
Permalink: http://link.aip.org/link/?JCPSA6/126/071101/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.Qv
    Stability and fragmentation of atomic and molecular clusters
  • 33.80.Gj
    Diffuse molecular spectra; predissociation, photodissociation
  • 33.80.Eh
    Autoionization, photoionization, and photodetachment of molecules
  • YEAR: 2007

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (39)
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  1. C. Mundy and I. Kuo, Chem. Rev. (Washington, D.C.) 106, 1282 (2006).
  2. T. Huthwelker, M. Ammann, and T. Peter, Chem. Rev. (Washington, D.C.) 106, 1375 (2006).
  3. M. J. Packer and D. C. Clary, J. Phys. Chem. 99, 14323 (1995).
  4. C. Lee, C. Sosa, M. Planas, and J. J. Novoa, J. Chem. Phys. 104, 7081 (1996).
  5. S. Re, Y. Osamura, Y. Suzuki, and H. F. Schaefer III, J. Chem. Phys. 109, 973 (1998).
  6. B. Gertner, G. Peslherbe, and J. Hynes, Isr. J. Chem. 39, 273 (1999).
  7. A. Milet, C. Struniewicz, R. Moszynski, and P. E. S. Wormer, J. Chem. Phys. 115, 349 (2001).
  8. C. Amirand and D. Maillard, J. Mol. Struct. 176, 181 (1988).
  9. S. Hurley, T. Dermota, D. Hydutsky, and A. Castleman, J. Chem. Phys. 118, 9272 (2003).
  10. M. Weimann, M. Fárník, and M. A. Suhm, Phys. Chem. Chem. Phys. 4, 3933 (2002).
  11. M. Fárník, M. Weimann, and M. A. Suhm, J. Chem. Phys. 118, 10120 (2003).
  12. K. Bolton and J. Pettersson, J. Am. Chem. Soc. 123, 7360 (2001).
  13. K. Bolton, J. Mol. Struct.: THEOCHEM 632, 145 (2003).
  14. A. Al-Halabi, R. Bianco, and J. Hynes, J. Phys. Chem. A 106, 7639 (2002).
  15. L. Wang and D. C. Clary, J. Chem. Phys. 104, 5663 (1996).
  16. B. J. Gertner and J. T. Hynes, Faraday Discuss. 110, 301 (1998).
  17. M. Svanberg, J. B. C. Pettersson, and K. Bolton, J. Phys. Chem. A 104, 5787 (2000).
  18. V. Buch, J. Sadlej, N. Aytemiz-Uras, and J. P. Devlin, J. Phys. Chem. A 106, 9374 (2002).
  19. J. Graham and J. Roberts, J. Phys. Chem. 98, 5974 (1994).
  20. H. Kang, T. H. Shin, S. C. Park, I. K. Kim, and S. J. Han, J. Am. Chem. Soc. 122, 9842 (2000).
  21. S. Park and H. Kang, J. Phys. Chem. B 109, 5124 (2005).
  22. J. Devlin, N. Uras, J. Sadlej, and V. Buch, Nature (London) 417, 269 (2002).
  23. F. Bournel, C. Mangeney, M. Tronc, C. Laffon, and P. Parent, Phys. Rev. B 65, 201404 (2002).
  24. F. Bournel, C. Mangeney, M. Tronc, C. Laffon, and P. Parent, Surf. Sci. 528, 224 (2003).
  25. P. Parent and C. Laffon, J. Phys. Chem. B 109, 1547 (2005).
  26. M. Kondo, H. Kawanowa, Y. Gotoh, and R. Souda, J. Chem. Phys. 121, 8589 (2004).
  27. A. L. Sobolewski and W. Domcke, J. Phys. Chem. A 107, 1557 (2003).
  28. U. Buck, J. Phys. Chem. A 106, 10049 (2002).
  29. R. Baumfalk, U. Buck, C. Frischkorn, S. R. Gandhi, and C. Lauenstein, Ber. Bunsenges. Phys. Chem. 101, 606 (1997).
  30. C. Bobbert, S. Schütte, C. Steinbach, and U. Buck, Eur. Phys. J. D 19, 183 (2002).
  31. S. W. Downey and R. S. Hozack, Opt. Lett. 14, 15 (1989).
  32. The background signal corresponds to the photolysis of rest gas molecules, namely, pump fluid hydrocarbons, and the photolysis of HBr molecules diffused from the pickup cell.
  33. R. Baumfalk, U. Buck, C. Frischkorn, N. H. Nahler, and L. Hüwel, J. Chem. Phys. 111, 2595 (1999).
  34. A. L. Sobolewski and W. Domcke, J. Chem. Phys. 122, 184320 (2005).
  35. A. L. Sobolewski and W. Domcke, Phys. Chem. Chem. Phys. 4, 4 (2002).
  36. The absolute signal intensities depend on many factors, e.g., laser power and its focusing into the TOF chamber, the pickup cell pressure, etc. Since the spectra are quite sensitive to some of these parameters, the relative intensities should be regarded as approximate. However, a ratio of [approximate]103 would be expected between the H-fragment signals from HBr(H2O) and HBr(D2O)n, if the H atom were “diluted” by charge transfer process in the (D2O)n cluster. In fact, the measured ratio is orders of magnitude smaller.
  37. J. Brudermann, U. Buck, and V. Buch, J. Phys. Chem. 106, 453 (2002).
  38. It should be noted that various structures of proton transfer states ranging from hydronium to a strongly stretched molecular halide can occur on the ice particle surface due to a range of microsolvation environments. The hydrogen in the intact HX molecule and in the hydronium ion represent two extreme cases. A high asymmetry in the hydronium structure would lead to a deposition of the excitation energy into a dissociative mode for the bridging hydrogen between halogen and oxygen atoms. This would lead to fast departing hydrogens and less isotopic mixing which are both not observed in the experiment. Therefore the structures close to hydronium are expected to dominate.
  39. S.-C. Park, K.-H. Jung, and H. Kang, J. Chem. Phys. 121, 2765 (2004).

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