Abstract
Supersonic free expansion has been utilized in the last years to prepare a wide variety of weakly bound molecular complexes which involve a rare-gas atom bound to a diatomic or a polyatomic molecule [1]. Of considerable interest is the nature of intramolecular dynamics of van der Waals molecules in vibrationally excited levels of the ground electronic state and in the electronically excited configurations. Recently, Kim, Smalley, Johnson, Wharton and Levy [2] have provided a pioneering study of the photodissociation dynamics of He I2, demonstrating the following:
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(a)
Photodissociation in the electronically excited B3π state of He I2 occurs via vibrational predissociation [2a].
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(b)
The vibrational predissociation rate of He I2 (B) depends almost quadratically on the vibrational quantum number v associated to the I-I stretch [2c]. The lifetimes varied from 221 psec. for v= 12 to 38 psec. for v=26 [2c].
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(c)
The propensity rule ΔV = -1 for vibrational predissociation of He I2 (B) was established [2b].
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References
See for example (a) T. R. Dyke, B. J. Howard, and W. Klemperer, J. Chem. Phys. 56, 2442 (1972); (b) S. E. Novick, K. C. Janda, S. L. Holmgren, M. Waldman, and W. Klemperer, J. Chem. Phys., 65, 1114 (1976); and references cited therein.
a) R. E. Smalley, D. H. Levy, and L. Wharton, J. Chem. Phys. 64, 3266 (1976); (b) M. S. Kim, R. E. Smalley, L. Wharton, and D. H. Levy, J. Chem. Phys. 65, 1216 (1976); (c) K. E. Johnson, L. Wharton, and D. H. Levy, to be published.
a) J. A. Beswick and J. Jortner, J. Chem. Phys. 68, 2277 (1978); (b) J. A. Beswick and J. Jortner, J. Chem. Phys. 69, 512 (1978); (c) J. A. Beswick, G. Delgado-Barrio and J. Jortner, to be published.
L. Fox, The Numerical Solution of Two-Point Boundary Value Problems in Ordinary Differential Equations, Oxford University Press, London, 1957. We are indebted to Dr J.M. Launay for providing us with his integrator.
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Beswick, J.A., Jortner, J. (1979). Photodissociation Lifetimes of Van der Waals Complexes. In: Kompa, K.L., Smith, S.D. (eds) Laser-Induced Processes in Molecules. Springer Series in Chemical Physics, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-67254-5_67
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DOI: https://doi.org/10.1007/978-3-642-67254-5_67
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