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Full Paper
Chemiluminescence of 1,2-dioxetanone studied by a closed-shell DFT approach
Article first published online: 8 JAN 2013
DOI: 10.1002/qua.24389
Copyright © 2013 Wiley Periodicals, Inc.
Additional Information
How to Cite
da Silva, L. P. and Esteves da Silva, J. C.G. (2013), Chemiluminescence of 1,2-dioxetanone studied by a closed-shell DFT approach. Int. J. Quantum Chem., 113: 1709–1716. doi: 10.1002/qua.24389
Publication History
- Issue published online: 6 MAY 2013
- Article first published online: 8 JAN 2013
- Manuscript Accepted: 17 DEC 2012
- Manuscript Revised: 14 DEC 2012
- Manuscript Received: 6 NOV 2012
Funded by
- Fundação para a Ciência e Tecnologia (FCT, Lisbon) [Programa Operacional Temático Factores de Competitividade (COMPETE) e comparticipado pelo Fundo Comunitário Europeu FEDER] (Project PTDC/QUI/71366/2006)
- FCT. Grant Number: SFRH/BD/76612/2011
Keywords:
- chemiluminescence;
- 1,2-dioxetanone;
- closed-shell approach;
- density functional theory;
- thermal decomposition
Abstract
The chemiluminescence of simple 1,2-dioxetanone has already been studied by both multiconfigurational and density functional theory calculations. The former approach revealed a step-wise biradical mechanism for its decomposition, whereas the latter revealed a concerted mechanism. The first approach was not in line with both computational and experimental findings, whereas the second mechanism was. Due to these apparent mechanistic contradictions and some concerns regarding our concerted mechanism, and the use of a closed-shell approach and different methods for geometry and single-point calculations, we have revisited the chemiluminescence of this molecule. Once again the concerted mechanism was found to be prevailing, and a closed-shell approach was able to rationalize the chemiluminescence of 1,2-dioxetanone. It was once again noted that an open-shell and a step-wise biradical mechanism cannot explain the chemiluminescence of this molecule. © 2013 Wiley Periodicals, Inc.