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

Research output: Contribution to journalReview article

Original languageEnglish
Pages (from-to)13880-13901
Number of pages22
JournalPhysical Chemistry Chemical Physics
Issue number26
Early online date16 Jan 2019
DateIn preparation - 2018
DateSubmitted - 5 Dec 2018
DateAccepted/In press - 16 Jan 2019
DateE-pub ahead of print - 16 Jan 2019
DatePublished (current) - 14 Jul 2019


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).

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