Issue 30, 2017

XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration

Abstract

Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (<7 fs) XUV pulses to produce excited cationic states of benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH3+ fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.

Graphical abstract: XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration

Article information

Article type
Paper
Submitted
07 Apr 2017
Accepted
15 Jun 2017
First published
19 Jun 2017

Phys. Chem. Chem. Phys., 2017,19, 19822-19828

XUV-induced reactions in benzene on sub-10 fs timescale: nonadiabatic relaxation and proton migration

M. C. E. Galbraith, C. T. L. Smeenk, G. Reitsma, A. Marciniak, V. Despré, J. Mikosch, N. Zhavoronkov, M. J. J. Vrakking, O. Kornilov and F. Lépine, Phys. Chem. Chem. Phys., 2017, 19, 19822 DOI: 10.1039/C7CP02255G

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