  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.
