Mechanistic study of the unimolecular decomposition of 1,2‐dioxetanedione |
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| Authors: | Luís Pinto da Silva Joaquim C. G. Esteves da Silva |
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| Affiliation: | Centro de Investiga??o em Química, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, , 4169‐007 Porto, Portugal |
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| Abstract: | The unimolecular decomposition of 1,2‐dioxetanedione, the high‐energy intermediate of the chemiluminescence peroxyoxalate reaction, was studied by theoretical means for the first time. Our calculations have provided results in line with the experimental data regarding this compound. 1,2‐Dioxetanedione decomposes due to a step‐wise biradical mechanism. In the biradical region of the decomposition path, there is a path for singlet chemiexcitation. Interactions between the singlet ground and excited states with triplet states can explain the weak unimolecular chemiluminescence of 1,2‐dioxetanedione. Copyright © 2013 John Wiley & Sons, Ltd. |
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| Keywords: | 1,2‐dioxetanedione chemiluminescence CIEEL ICIC interstate crossing peroxyoxalate system step‐wise biradical unimolecular decomposition |
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