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Connection between the direct and mapping forms of a factorized classical propagator

Loss of chlorine in mass spectra of DCl picked up by water clusters in a beam

J. Chem. Phys. 124, 146102 (2006); doi:10.1063/1.2188938

Published 13 April 2006

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Ramiro Moro, Roman Rabinovitch, and Vitaly V. Kresin
Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089-0484
Water clusters (H2O)n, n<=16, are produced by supersonic expansion of water vapor into vacuum, and then pick up a DCl molecule. The resulting mixed clusters are analyzed by electron bombardment ionization mass spectrometry. In all cases observed, the chlorine atom is lost in the ionization process, producing a deuterated water cluster cation [(H2O)nD+]. This suggests that the chlorine atom stays on the surface and has a weaker bond to the host cluster. ©2006 American Institute of Physics
History: Received 25 January 2006; accepted 27 February 2006; published 13 April 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/146102/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.Mr
    Spectroscopy and geometrical structure of atomic and molecular clusters
  • 33.15.Ta
    Molecular mass spectra
  • 34.80.Gs
    Molecular excitation and ionization by electron impact
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • YEAR: 2006

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (13)
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  1. R. Moro, R. Rabinovitch, and V. V. Kresin, J. Chem. Phys. 123, 074301 (2005).
  2. S.-C. Park, K.-H. Jung, and H. Kang, J. Chem. Phys. 121, 2765 (2004).
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  6. In pick-up experiments, the probability that a cluster acquires k guest molecules is commonly approximated by the Poisson distribution, P(k)=<k>ke–<k>/k!, where <k> is the average. This distribution predicts that when <k>=1 (primarily single molecule pickup) the pure peak is at P(0)=e–1=0.37 of its original intensity. Based on this estimate, we adjusted the DCl pressure to obtain a 60% depletion in the pure water cluster peak. Under these conditions one would expect P(1)=P(0); however, in the actual mass spectrum the intensity of mixed clusters is below that of the pure water peak. We assign this difference primarily to the fact that the relatively light water clusters are scattered and deflected in the totally inelastic collision, so that only a fraction of the mixed species is actually detected (this fraction decreases with decreasing cluster size and with increasing k).
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  9. We should note that in the case of a water cluster picking up a water molecule the kinetic energy deposited is [approximate]4n/(n+1)  kcal/mol, which is higher than what we estimated in Ref. 1 due to an error in the speed calibration.
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