Abstract
A brief review of the structure and dynamics of the rare gas halogen van der Waals molecules is given. New results are presented for the lifetimes of several vibrational levels of the B state of NeBr2. Also presented for the first time are the branching ratios into the possible product channels upon vibrational predissociation of NeBr2. Most of the molecules have structures not too different from what one would obtain by bringing the rare gas atom into van der Waals contact with the two halogen atoms. ArClF and KrClF are exceptions to this trend. They are linear molecules with a van der Waals bond length substantially shorter than the sum of atomic van der Waals radii. The dynamics observed for NeBr2 are not too different from what one would have predicted on the basis of earlier HeI2 results. For lower vibrational levels the Δv = -−1 channel predominates and only a modest fraction of the product kinetic energy is transferred to the rotational degree of freedom. For higher vibrational levels (near v = 28) the Δv = −1 channel closes and increasing values for Δv are observed. Analysis of this data yields a value for the X state Do of 70.5 ± 2.0 cm−1.
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References
S. J. Harris, S. E. Novick and W. Klemperer, J. Chem, Phys. 61, 193, (1974).
S. E. Novick, S. J. Harris, K. C. Janda and W. Klemperer, Canadian J. Phys. 53 2007, (1975).
S. E. Novick, K. C. Janda and W. Klemperer, J. Chem. Phys. 65, 5115, (1977).
F. A. Baiocchi, T. A. Dixon and W. Klemperer, J. Chem. Phys. 77, 1632, (1982).
D. H. Levy, Adv. Chem. Phys. 47, 323, (1981).
W. Sharfin, P. Kroger, and S. C. Wallace, Chem. Phys. Letts., 85, 81, (1982).
J. C. Drobits, J. M. Skene and M. I. Lester, J. Chem. Phys., 84, 2896, (1986).
The HeCl2 well depth was obtained by solving for the Do level of the HeCl2 potential obtained by differential scattering studies. B. P. Reid, unpublished results.
J. I. Cline, D. D. Evard, F. Thommen and K. C. Janda, J. Chem. Phys., 84, 1165 (1986).
L. J. van de Burgt, J. P. Nicolai, and M. C. Heaven, J. Chem. Phys., 81, 5514 (1984).
J. I. Cline, N. Sivakumar, D. E. Evard, and K. C. Janda, to be published.
D. D. Evard, F. Thommen, and K. C. Janda, J. Chem. Phys. 84, 3630 (1986).
B. A. Swartz, D. E. Brinza, C. M. Western, and K. C. Janda, J. Phys. Chem. 84, 6272 (1984).
F. Thommen, D. D. Evard and K. C. Janda, J. Chem. Phys. 82, 5295 (1985).
N. Sivakumar, J. I. Cline, D. D. Evard, and K. C. Janda, to be published.
The bond energies quoted for ArClF and KrClF are De values taken from ref. 2. These were obtained by fitting 6,12 type potentials to centrifugal distortion constants. The errors involved in these calculations are difficult to estimate.
J. C. Drobits and M. I. Lester, to be published.
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules, Van Nostrand, New York, 1979.
G. C. Pimentel and R. D. Spratley, Understanding Chemistry, Holden-Day Inc., San Francisco, 1971.
J. A. Beswick and J. Jortner, Adv. Chem. Phys. 47, 323 (1981).
G. E. Ewing, Faraday Discuss. Chem. Soc. 73, 325 (1982).
D. E, Brinza, B. A. Swartz, C. M. Western and K. C. Janda, J. Chem. Phys. 79, 1541 (1983).
J. M. Skene, J. C. Drobits and M. T. Lester, J. Cham. Phys. 85, 2329 (1986).
D. E. Brinza, C. M. Western, D. D. Evard, F. Thommen, B. A. Swartz, and K. C. Janda, J. Phys. Chem. 88, 2004 (1984).
J. A. Coxon, J. Quant. Spectrosc. Radiat. Transfer, 12, 639 (1972).
B. A. Swartz, Ph.D. Thesis, California Institute of Technology, 1984.
M. C. Heaven, Molecular Spectroscopy, Chem. See. Spec. Per. Rep., The Chemical Society, London, in press.
T. D. Russell, B. M. DeKoven, J. A. Blazy, and D. H. Levy, J. Chem. Phys. 72, 3001 (1980).
M. Siese, E. Tiemann, and U. Wulf, Chem. Phys. Lett. 117, 208 (1985).
J. E. Kenny, K. E. Johnson, W. Sharfin, and D. H. Levy, J. Chem. Phys. 72, 1109, (1980).
J. A. Blazy, B. M. DeKoven, T. D. Russell, and D. H. Levy, J. Chem. Phys. 72, 2439 (1980).
W. Sharfin, K. E. Johnson, L. Wharton, and D. H. Levy, J. Chem. Phys. 71, 1292 (1979).
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© 1987 D. Reidel Publishing Company
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Cline, J.I., Evard, D.D., Reid, B.P., Sivakumar, N., Thommen, F., Janda, K.C. (1987). Structure and Dynamics of the Rare Gas-Halogen Van Der Waals Molecules: Product State Distributions for Vibrational Predissociation of NeBr2 . In: Weber, A. (eds) Structure and Dynamics of Weakly Bound Molecular Complexes. NATO ASI Series, vol 212. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3969-1_39
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DOI: https://doi.org/10.1007/978-94-009-3969-1_39
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