Vibrational predissociation of Ar ⋅ BCl3: A Monte Carlo-RRKM study

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Abstract
Experiments have shown that absorption of a single photon by the high‐frequency asymmetric stretching mode of boron trichloride will lead to dissociation of the Ar ⋅ BCl3 van der Waals molecule in 1–3 ps. Since it appears unlikely that a direct dynamical coupling of the excited mode to the weak van der Waals bond occurs, it is somewhat difficult to understand why the observed lifetime of the metastable complex is so short. One finds, however, that an RRKM calculation (performed within a Monte Carlo framework) correctly predicts that a short lifetime will be observed, suggesting that energy randomization amongst the low‐frequency modes of oscillation may play an important role in the predissociation dynamics.