Benoit Mignolet
Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection
Mignolet, Benoit; Curchod, Basile F.E.; Martinez, Todd J.
Abstract
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.
Citation
Mignolet, B., Curchod, B. F., & Martinez, T. J. (2016). Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection. Angewandte Chemie International Edition, 55(48), 14993-14996. https://doi.org/10.1002/anie.201607633
Journal Article Type | Article |
---|---|
Acceptance Date | Sep 13, 2016 |
Online Publication Date | Oct 26, 2016 |
Publication Date | Nov 21, 2016 |
Deposit Date | Nov 6, 2017 |
Publicly Available Date | Dec 8, 2017 |
Journal | Angewandte Chemie International Edition |
Print ISSN | 1433-7851 |
Electronic ISSN | 1521-3773 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 55 |
Issue | 48 |
Pages | 14993-14996 |
DOI | https://doi.org/10.1002/anie.201607633 |
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Copyright Statement
This is the peer reviewed version of the following article: Mignolet, Benoit, Curchod, Basile F. E. & Martinez, Todd J. (2016). Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection. Angewandte Chemie International Edition 55(48): 14993-14996, which has been published in final form at https://doi.org/10.1002/anie.201607633. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.
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