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How Do Methyl Groups Enhance the Triplet Chemiexcitation Yield of Dioxetane?
journal contribution
posted on 2017-07-27, 00:00 authored by Morgane Vacher, Pooria Farahani, Alessio Valentini, Luis Manuel Frutos, Hans O. Karlsson, Ignacio Fdez. Galván, Roland LindhChemiluminescence
is the emission of light as a result of a nonadiabatic
chemical reaction. The present work is concerned with understanding
the yield of chemiluminescence, in particular how it dramatically
increases upon methylation of 1,2-dioxetane. Both ground-state and
nonadiabatic dynamics (including singlet excited states) of the decomposition
reaction of various methyl-substituted dioxetanes have been simulated.
Methyl-substitution leads to a significant increase in the dissociation
time scale. The rotation around the O–C–C–O dihedral
angle is slowed; thus, the molecular system stays longer in the “entropic
trap” region. A simple kinetic model is proposed to explain
how this leads to a higher chemiluminescence yield. These results
have important implications for the design of efficient chemiluminescent
systems in medical, environmental, and industrial applications.
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ground-statedecomposition reactionMethyl-substitutionnonadiabatic dynamicsnonadiabatic chemical reactionmethyl-substituted dioxetanesentropicMethyl Groups EnhanceapplicationChemiluminescenceimplicationchemiluminescent systemsdihedralemissionunderstandingchemiluminescenceTriplet Chemiexcitation YieldsingletmodelDioxetanerotationmethylationregiontrapdissociation time scale
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