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Rostock 2019 – scientific programme

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MO: Fachverband Molekülphysik

MO 11: Photochemistry

MO 11.7: Talk

Wednesday, March 13, 2019, 12:15–12:30, S HS 001 Biologie

Controlling the dynamics of the photodissociation of diphenylmethyl bromide — •Franziska Schüppel, Matthias K. Roos, and Regina de Vivie-Riedle — Department Chemie, Ludwig-Maximilians-Universität München

Carboradicals and -cations are key intermediates for many chemical reactions and can be generated by UV-laser excitation from certain precursor molecules. Recently, we investigated the photodissociation of diphenylmethyl bromide using quantum dynamics simulations. [1] The dynamics is characterized by two consecutive conical intersections (CoIns) with the first one leading to the favored homolytic dissociation channel.

The control of the ratio of homolytic and heterolytic bond cleavage is of major interest for chemical applications. By using a second few-cycle IR laser pulse it is possible to create a superposition of a wave packet at a CoIn and by that control the population transfer through that CoIn. [2] We want to apply such a laser pulse to diphenylmethyl bromide to explore to which extend the population transfer of the wave packet through the first CoIn can be disabled. By that we want to regulate the branching between carbocation and carboradical formation.

[1] F. Schüppel et al., PCCP 20 (2018), 22753-22761.

[2] P. von den Hoff et al., PCCP 14 (2012), 14460-14485.

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