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Schüppel, Franziska; Roos, Matthias K.; Vivie-Riedle, Regina de (2018): Ultrafast non-adiabatic dynamics of excited diphenylmethyl bromide elucidated by quantum dynamics and semi-classical on-the-fly dynamics. In: Physical Chemistry Chemical Physics, Vol. 20, No. 35: pp. 22753-22761
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Carbocations and carboradicals are key intermediates in organic chemistry. Typically UV laser excitation is used to induce homolytical or heterolytical bond cleavage in suitable precursor molecules. Of special interest hereby are diphenylmethyl compounds (Ph2CH-X) with X = Cl, Br as a leaving group as they form diphenylmethyl radicals (Ph2CH) and cations (Ph2CH+) within a femtosecond time scale in polar solvents. In this work, we build on our methodology developed for the chlorine case and investigate the photodissociation reaction of Ph2CH-Br by state-of-the-art theoretical methods. On the one hand, we employ specially adapted reactive coordinates for a grid-based wave packet dynamics in reduced dimensionality using the Wilson G-matrix ansatz for the kinetic part of the Hamiltonian. On the other hand, we use full-dimensional semiclassical on-the-fly dynamics with Tully's fewest switches surface hopping routine for comparison. We apply both methods to explain remarkable differences in experimental transient absorption measurements for Cl or Br as the leaving group. The wave packet motion, visible only for the bromine leaving group, can be related to the crucial role of the central carbon atom, which undergoes rehybridization from sp(3) to sp(2) during the photoinduced bond cleavage. Comparable features are the two consecutive conical intersections near the Franck-Condon region controlling the product splitting to Ph2CH/Br and Ph2CH+/Br- as well as the difference in delay time for the respective product formation.