Wave Packet Simulation of Nonadiabatic Dynamics in Highly Excited 1,3-Dibromopropane

Rasmus Y. Brogaard, Klaus Braagaard Møller, Theis Ivan Sølling

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We have conducted wave packet simulations of excited-state dynamics of 1,3-dibromopropane (DBP) with the aim of reproducing the experimental results of the gas-phase pump-probe experiment by Kotting et al. [Kotting. C.; Diau, E. W.-G.; Solling, T. L. Zewail, A. H. J. Phys. Chem. A 2001106, 7530]. In the experiment. DBP is excited to a Rydberg state 8 eV above the ground state. The interpretation of the results is that a torsional motion of the bromomethylene groups with a vibrational period of 680 is is activated upon excitation. The Rydberg state decays to a valence state, causing a dissociation of one of the carbon bromine bonds oil a time scale of 2.5 ps. Building the theoretical framework for the wave packet propagation around this model of the reaction dynamics, the Simulations reproduce, to a good extent, the time scales observed in the experiment. Furthermore. the Simulations provide insight into how the torsion motion influences the bond breakage, and C we can conclude that the mechanism that delays the dissociation is solely the electronic transition from the Rydberg state to the valence state and does not involve, for example, intramolecular vibrational energy redistribution (IVR).
Original languageEnglish
JournalJournal of Physical Chemistry A
Issue number42
Pages (from-to)10481-10486
Publication statusPublished - 2008

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