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Issue 2, 2014
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A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine

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Abstract

How much time does it take for a wavepacket to roam on a multidimensional potential energy surface? This combined theoretical and pump–probe femtosecond time experiment on 2-hydroxypyridine proposes an answer. Bypassing the well-established transition state and conical intersection relaxation pathways, this molecular system undergoes relaxation into the S1 excited state: the central ring is destabilized by the electronic excitation, within ∼100 fs after absorption of the pump photon, then the H-atom bound to oxygen undergoes a roaming behavior when it couples to other degrees of freedom of the molecule. The timescale of the latter process is measured to be ∼1.3 ps. Further evolution of the wavepacket is either an oscillation onto the S1 potential or a conversion into the triplet state for timescale larger than ∼110 ps. Our work introduces a new tool for the understanding of time-resolved relaxation dynamics applied to large molecules through the roaming dynamics characterized by its strongly delocalized wavepacket on flat molecular potential energy surfaces.

Graphical abstract: A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine

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Publication details

The article was received on 12 Jul 2013, accepted on 18 Oct 2013 and first published on 18 Oct 2013


Article type: Paper
DOI: 10.1039/C3CP52923A
Citation: Phys. Chem. Chem. Phys., 2014,16, 581-587
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    A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine

    L. Poisson, D. Nandi, B. Soep, M. Hochlaf, M. Boggio-Pasqua and J. Mestdagh, Phys. Chem. Chem. Phys., 2014, 16, 581
    DOI: 10.1039/C3CP52923A

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