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Issue 26, 2019
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Photoinduced C–H bond fission in prototypical organic molecules and radicals

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Abstract

Recent experimental and computational advances have heralded huge progress in the range and the detail of the database pertaining to photoinduced C–H bond fission processes. This Perspective provides a snapshot of the current state of knowledge as determined via gas phase (i.e. isolated molecule) studies of the primary photochemistry of families of hydrocarbon molecules (alkynes, alkenes, alkanes, aromatics and selected heteroatom containing analogues) and the corresponding radicals (including saturated and unsaturated hydrocarbon radicals). Different families show different and, in many cases, understandable propensities for dissociating from an excited electronic state or following non-adiabatic coupling (i.e. internal conversion) to high vibrational levels of the ground electronic state. The Perspective seeks to emphasise the potentially vast range of behaviours (dissociation timescales, product energy disposals, etc.) that can be expected to accompany internal conversion, reflecting the extent to which the tuning coordinate (i.e. the nuclear motions that tune the energy separation between the excited and ground state) projects onto the dissociation coordinate of interest (i.e. the breaking of the C–H bond).

Graphical abstract: Photoinduced C–H bond fission in prototypical organic molecules and radicals

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Article information


Submitted
05 Dec 2018
Accepted
16 Jan 2019
First published
16 Jan 2019

Phys. Chem. Chem. Phys., 2019,21, 13880-13901
Article type
Perspective
Author version available

Photoinduced C–H bond fission in prototypical organic molecules and radicals

M. N. R. Ashfold, R. A. Ingle, T. N. V. Karsili and J. Zhang, Phys. Chem. Chem. Phys., 2019, 21, 13880
DOI: 10.1039/C8CP07454B

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