Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection

Mignolet, Benoit; Curchod, Basile F.E.; Martinez, Todd J.

doi:10.1002/anie.201607633

Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection

Mignolet, Benoit; Curchod, Basile F.E.; Martinez, Todd J.

Authors

Benoit Mignolet

Dr Basile Curchod basile.f.curchod@durham.ac.uk
Academic Visitor

Todd J. Martinez

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.