| Full text | |
| Author(s): |
Vacher, Morgane
;
Farahani, Pooria
;
Valentini, Alessio
;
Frutos, Luis Manuel
;
Karlsson, Hans O.
;
Galvan, Ignacio Fdez.
;
Lindh, Roland
Total Authors: 7
|
| Document type: | Journal article |
| Source: | Journal of Physical Chemistry Letters; v. 8, n. 16, p. 3790-3794, AUG 17 2017. |
| Web of Science Citations: | 7 |
| Abstract | |
Chemiluminescence 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. (AU) | |
| FAPESP's process: | 15/02314-8 - Theoretical and experimental studies on the chemiexcitation efficiency of cyclic peroxide decomposition |
| Grantee: | Pooria Farahani |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |