title: Changes of structure and energy on the route from dioxetane to carbonyl products. A quantum chemical study.
abstract: Energy diagrams, changes of geometry and bond orders were calculated semi-empirically for the thermolysis of 1,2-dioxetane. Stretching of the O-O bond, then of the C-C bond and distortion of the whole quadrangular structure make major, but different, contributions to the reaction coordinate on the path to formaldehyde. The activation barrier represents a vast region where the gaps between the ground and excited states are small, and this favours horizontal radiationless transitions leading to the excitation of a product. The results show that semi-empirical calculations may help to provide better insight into the nature and mechanism of the chemiluminescence excitation.
authors.affiliation: Institute of Biochemical Physics, United Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia.
authors.forename: R F
authors.initials: RF
authors.lastname: Vasil'ev
mesh_terms: D006571:Heterocyclic Compounds / Q000737:chemistry*; D006573:Heterocyclic Compounds, 1-Ring; D008163:Luminescent Measurements; D015394:Molecular Structure; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D006571:Heterocyclic Compounds; D006573:Heterocyclic Compounds, 1-Ring; C079142:1,2-dioxetane