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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2014

A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.

Résumé

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.
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Dates et versions

hal-00915277 , version 1 (06-12-2013)

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L. Poisson, Dhananjay Nandi, Benoît Soep, Majdi Hochlaf, Martial Boggio-Pasqua, et al.. A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.. Physical Chemistry Chemical Physics, 2014, 16 (2), pp.581-7. ⟨10.1039/c3cp52923a⟩. ⟨hal-00915277⟩
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