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Triplet versus singlet chemiexcitation mechanism in dioxetanone: a CASSCF/CASPT2 study

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Abstract

Chemiluminescence is a fundamental process of chemistry consisting in the conversion of chemical energy stored in chemical bonds into light. It is used by nature and by man-made technology, being especially relevant in chemical analysis. The understanding of the phenomenon strongly relies in the study of peroxide models such as 1,2-dioxetanones. In the present contribution, the singlet S 2 and the triplet T 2 potential energy surfaces of the unimolecular decomposition of 1,2-dioxetanone have been mapped along the O–O and C–C bond coordinates on the grounds of the multiconfigurational CASPT2//CASSCF approach. Results confirm the energy degeneracy between T 2, T 1, S 1, and S 0 at the TS region, whereas S 2 is unambiguously predicted at higher energies. Triplet-state population is also supported by the spin–orbit couplings between the singlet and triplet states partaking in the process. In particular, the first-principle calculations show that decomposition along the T 2 state is a competitive process, having a small (~3 kcal/mol) energy barrier from the ground-state TS structure. The present findings can explain the higher quantum yield of triplet-state population with respect to the excited singlet states recorded experimentally for the unimolecular decomposition of 1,2-dioxetanone models.

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Acknowledgements

This research was supported by Projects CTQ2014-58624-P of the Spanish MINECO/FEDER. D.R.-S. thanks the “Juan de la Cierva” program of the Spanish MINECO (Ref. JCI-2012-13431). A.F.-M. thanks BES-2011-048326 FPI Grant and the EEBB-I-14-08821 mobility program (MINECO). I.F.G. and R.L. acknowledge financial support from the Swedish Research Council (Grant No. 2012-3910), the eSSENCE program, and Uppsala University.

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  1. Institut de Ciència Molecular, Universitat de València, P.O. Box 22085, 46071, Valencia, Spain

    Antonio Francés-Monerris & Daniel Roca-Sanjuán

  2. Department of Chemistry-Ångström, Uppsala Center for Computational Chemistry, UC3, Uppsala University, Uppsala, Sweden

    Antonio Francés-Monerris, Ignacio Fdez. Galván & Roland Lindh

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  1. Antonio Francés-Monerris
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  2. Ignacio Fdez. Galván
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  3. Roland Lindh
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Correspondence to Roland Lindh or Daniel Roca-Sanjuán.

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Published as part of the special collection of articles derived from the 10th Congress on Electronic Structure: Principles and Applications (ESPA-2016).

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Francés-Monerris, A., Fdez. Galván, I., Lindh, R. et al. Triplet versus singlet chemiexcitation mechanism in dioxetanone: a CASSCF/CASPT2 study. Theor Chem Acc 136, 70 (2017). https://doi.org/10.1007/s00214-017-2095-x

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