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The probability of vibrational relaxation of a number of molecules is known to increase at lower temperatures. The role of intermediate complexes in such processes is discussed. A model similar to one previously introduced by Tully and co-workers is used to describe complex formation and decay. An orbiting capture cross section is assumed, and unimolecular theory is used to estimate the rate of vibrational predissociation. Fair agreement with a large body of experimental data is obtained.
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Robert J. Gordon (1981) studied this question.
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