Ultrafast 25-fs relaxation in highly excited states of methyl azide mediated by strong nonadiabatic coupling

[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

Available on ORBi :

since 17 December 2017

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