VIBRATIONAL ENERGY TRANSFER IN LIQUIDS

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1975

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Ohio State University

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Vibrational relaxation times in liquids can range over 12 orders of magnitude: Our own work1 on liquid nitrogen yields a VT relaxation time of 1 sec while for CH3CCl3 and other small organic molecules VV relaxation is ∼102−1 sec.2 These and other data appear consistent with a sample model3 which essentially treats the liquid as a high density gas where isolated binary collisions cause vibrational relaxation. Further tests of the binary collision model are most convincing from measurements of simple liquid systems. We have Just measured the vibrational relaxation time of liquid N2 doped with CH4, CO and O2 at 77∘K by pulsed laser and spectroscopic techniques. Rate constants for VV energy transfer from N2 to the dopants and VT relaxation times have been obtained. These rates are all consistent with the binary collision model.

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1 W. Calaway and G. Ewing, Chem. Phys. Lett. (1975) (in press). 2 A. Laubereau, D. von der Linde, and W. Kaiser, Phys. Rev. Lett. 28, 1162 (1972). 3 T. A. Litovitz, J. Chem. Phys. 26, 469 (1957).""


Author Institution: Argonne National Laboratory; Department of Chemistry, Indiana University

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