Photochemistry of dibromine peroxide, BrOOBr
The photochemistry of dibromine peroxide was investigated by means of mixed quantum-classical trajectory calculations on seven coupled potential energy surfaces. Photoexcited BrOOBr disintegrates rapidly, at a rate comparable with thermal decomposition. The rate constant is <i>J</i> = 9.7 × 10<sup>-2</sup> s<sup>-1</sup>. The mechanism was investigated, and the final photolysis products are shown to be mainly 2Br + O<sub>2</sub>, though there is a minor channel leading to 2BrO. Their formation involves an unusual intermolecular vibronic energy redistribution process. A hitherto unknown isomer of BrOOBr, the van der Waals complex O<sub>2</sub>(a<sup>1</sup>Δ<sub>g</sub>)·Br<sub>2</sub>(X<sup>1</sup>Σ+g), was found, which is more stable than the peroxide by 1.2 mE<sub>h</sub>.
Authors
- Alexander Alijah (ORCID: https://orcid.org/0000-0002-4915-0558)
- Najoua Derbel (ORCID: https://orcid.org/0000-0002-1400-3283)
- Thibaud Cours (ORCID: https://orcid.org/0000-0002-1326-5548)
- Wiem Chebbi (ORCID: https://orcid.org/0009-0009-0121-8929)
Institutions
- Tunis University (TN)
- Centre National de la Recherche Scientifique (FR)
- University of Carthage (TN)
- Groupe de Spectrométrie Moléculaire et Atmosphérique (FR)
- Tunis El Manar University (TN)
- Université de Reims Champagne-Ardenne (FR)
Publication Details
- Journal
- Physical Chemistry Chemical Physics
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5cp02124c
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Ministère de l’Enseignement Supérieur et de la Recherche Scientifique
- Ministère de l'Europe et des Affaires Étrangères
- Ministère de l'Education Nationale, de l'Enseignement Superieur et de la Recherche