6533b85efe1ef96bd12bfcb3
RESEARCH PRODUCT
Revisiting the Nonadiabatic Process in 1,2-Dioxetane.
Daniel Roca-sanjuánRoland LindhFelipe ZapataPooria Farahanisubject
Ab initio molecular dynamicschemistry.chemical_compound12-DioxetanechemistryComputational chemistryQuantum mechanicsTheoretical chemistrySinglet statePhysical and Theoretical ChemistryHigh ratioComputer Science Applicationsdescription
Determining the ground and excited-state decomposition mechanisms of 1,2-dioxetane is essential to understand the chemiluminescence and bioluminescence phenomena. Several experimental and theoretical studies has been performed in the past without reaching a converged description. The reason is in part associated with the complex nonadiabatic process taking place along the reaction. The present study is an extension of a previous work (De Vico, L.; Liu, Y.-J.; Krogh, J. W.; Lindh, R. J. Phys. Chem. A 2007, 111, 8013-8019) in which a two-step mechanism was established for the chemiluminescence involving asynchronous O-O' and C-C' bond dissociations. New high-level multistate multi configurational reference second-order perturbation theory calculations and ab initio molecular dynamics simulations at constant temperature are performed in the present study, which provide further details on the mechanisms and allow to rationalize further experimental observations. In particular, the new results explain the high ratio of triplet to singlet dissociation products.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2015-11-24 | Journal of chemical theory and computation |