Unimolecular Dissociation of CH-CCl Complex and Effect of Mode-Mode Coupling.

J Phys Chem A

Department of Chemistry, National Institute of Technology Meghalaya, Shillong 793003, Meghalaya, India.

Published: July 2021

The unimolecular dissociation dynamics of the CH-CCl (Bz-HCB) complex is studied with initial excitation of all vibrational modes for a temperature range of 1000-2000 K and with mode-specific excitations at 1500 K. The results are compared with those of the CH-CF [Bz- HFB] complex. When all modes of Bz-HCB are initially excited, the rate of dissociation is slower with respect to Bz-HFB. However, the rate of dissociation is faster when simulations with nonrandom excitation of the specific vibrational modes are performed. The rate of dissociation of Bz-HCB is found to become slower when a few intramolecular modes are excited along with all inter-fragment modes compared to the simulation when only inter-fragment modes of the same complex are excited. Such an energy-transfer dynamics is absent if both intramolecular and inter-fragment modes are not initially excited. Thus, a "stimulated" resonance energy-transfer dynamics is observed in Bz-HCB dissociation dynamics.

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http://dx.doi.org/10.1021/acs.jpca.1c01851DOI Listing

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