Article (Scientific journals)
Rich Athermal Ground‐State Chemistry Triggered by Dynamics through a Conical Intersection
Mignolet, Benoît; Curchod, Basile; Martínez, Todd J.
2016In Angewandte Chemie International Edition, 128 (48), p. 15217-15220
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Abstract :
[en] A fundamental tenet of statistical rate theories (such as transition state theory and RRKM) is the rapidity of vibrational relaxation. Excited-state reactions happen quite quickly (sub-picosecond) and thus can exhibit nonstatistical behavior. However, it is often thought that any diversity of photoproducts results from different conical intersections connecting the excited and ground electronic states. It is also conceivable that the large energy of the photon, which is converted to vibrational energy after electronic transitions could lead to athermal hot ground state reactions and that these might be responsible for the diversity of photoproducts. Here we show that this is the case for sulfines, where a single conical intersection is implicated in the electronic transition but the excited state reaction leads to nine different products within less than a picosecond.
Disciplines :
Chemistry
Author, co-author :
Mignolet, Benoît ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Curchod, Basile
Martínez, Todd J.
Language :
English
Title :
Rich Athermal Ground‐State Chemistry Triggered by Dynamics through a Conical Intersection
Publication date :
2016
Journal title :
Angewandte Chemie International Edition
ISSN :
1433-7851
eISSN :
1521-3773
Publisher :
John Wiley & Sons, United Kingdom
Volume :
128
Issue :
48
Pages :
15217-15220
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, Office of Science, US Department of Energy.
BAEF - Belgian American Educational Foundation [BE]
WBI - Wallonie-Bruxelles International [BE]
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