Rich Athermal Ground‐State Chemistry Triggered by Dynamics through a Conical Intersection. Issue 48 (26th October 2016)

• Record Type: Journal Article
• Authors: Mignolet, Benoit; Curchod, Basile F. E.; Martínez, Todd J.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 48(2016)
• Page Start: 14993
• Page End: 14996
• Publication Date: 2016-10-26
• Subjects: ab initio multiple spawning (AIMS) -- excited-state dynamics -- molecular dynamics -- oxathiirane -- photochemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201607633
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : An outlaw molecule : Theoretical studies show that sulfine exhibits an incredibly rich chemistry upon light‐irradiation, challenging the traditional view of photochemical and photodecomposition reactions due to highly nonstatistical behavior.