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Quantifying rival bond fission probabilities following photoexcitation: C-S bond fission in t-butylmethylsulfide

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)5290-5298
Number of pages9
JournalChemical Science
Early online date23 Apr 2019
DateAccepted/In press - 23 Apr 2019
DateE-pub ahead of print - 23 Apr 2019
DatePublished (current) - 22 May 2019


We illustrate a new, collision-free experimental strategy that allows determination of the absolute probabilities of rival bond fission processes in a photoexcited molecule – here t-butylmethylsulfide (BSM). The method combines single photon (‘universal’) ionization laser probe methods, simultaneous imaging of all probed fragments (multi-mass ion imaging) and the use of an appropriate internal calibrant (here dimethylsulfide). Image analysis allows quantification of the dynamics of the rival B–SM and BS–M bond fission processes following ultraviolet (UV) excitation of BSM and shows the former to be twice as probable, despite the only modest (∼2%) differences in the respective ground state equilibrium C–S bond lengths or bond strengths. Rationalising this finding should provide a stringent test of the two close-lying, coupled excited states of 1A′′ symmetry accessed by UV excitation in BSM and related thioethers, of the respective transition dipole moment surfaces, and of the geometry dependent non-adiabatic couplings that enable the rival C–S bond fissions.

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    Rights statement: This is the final published version of the article (version of record). It first appeared online via The Royal Society of Chemistry at 10.1039/c9sc00738e . Please refer to any applicable terms of use of the publisher.

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    Licence: CC BY


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