[en] Highly excited states of neutral molecules behave qualitatively differently than the lower excited states that are commonly studied in photochemistry. Such states are involved in ionospheric and astrochemical phenomena, as well as in detonation processes. However, highly excited states are poorly understood due to experimental and theoretical challenges in probing their complex dynamics. Here, we apply vacuum-UV femtosecond laser sources and an imaging photoelectron–photoion coincidence spectrometer to directly probe the surprisingly fast 25-fs reaction pathway of the energetic molecule methyl azide. Combined with advanced calculations, we conclude that the electronic relaxation is driven by strong nonadiabatic coupling and that population transfer occurs along a seam well above the minimum energy conical intersection.
Disciplines :
Chemistry
Author, co-author :
Peters, William K.
Couch, David E.
Mignolet, Benoît ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Shi, Xuetao
Nguyen, Quynh L.
Fortenberry, Ryan C.
Schlegel, H. Bernhard
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Kapteyn, Henry C.
Murnane, Margaret M.
Li, Wen
Language :
English
Title :
Ultrafast 25-fs relaxation in highly excited states of methyl azide mediated by strong nonadiabatic coupling
Publication date :
2017
Journal title :
Proceedings of the National Academy of Sciences of the United States of America
ISSN :
0027-8424
eISSN :
1091-6490
Publisher :
National Academy of Sciences, Washington, United States - District of Columbia
Peer reviewed :
Peer Reviewed verified by ORBi
Tags :
CÉCI : Consortium des Équipements de Calcul Intensif
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique
Funding text :
This work was supported by Department of Energy Office of Basic Energy Sciences Grant DE-SC0012628; Consortium des Equipements de Calcul Intensif for Computational Resources Grant FNRS 2.5020.11
Commentary :
B.M. and F.R. were supported by the Fonds National de la Recherche Scientifique (FNRS), Belgium
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