The mechanism of vibrational relaxation and dissociation in the O2–O system at elevated temperatures is investigated by means of molecular dynamics. The most recent O3 potential energy surfaces (PESs), obtained from the first principles quantum mechanical calculations [Varga et al., J. Chem. Phys. 147, 154312 (2017)], are used to derive a complete set of state-specific rate coefficients of vibrational energy transfer and dissociation. Unlike most of the previous efforts that utilize only the lowest and supposedly most reactive 11A′ O3 PES [A. Varandas and A. Pais, Mol. Phys. 65, 843 (1988)], this paper demonstrates the necessity to account for a complete ensemble of all excited O3 PESs that correlate with O2(X) and O(3P) when high-temperature kinetics is of interest. At the same time, it is found that the Varandas 11A′ O3 PES adequately describes vibrational energy transfer and dissociating dynamics when compared to the most recent 11A′ O3 PES by Varga et al. [J. Chem Phys. 147, 154312 (2017)]. The differences between this new dataset and previous rate coefficients are quantified by the master equation model.
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31 January 2020
Research Article|
January 23 2020
The importance of O3 excited potential energy surfaces in O2–O high-temperature kinetics
J. Chem. Phys. 152, 044305 (2020)
Article history
Received:
December 10 2019
Accepted:
January 09 2020
Citation
Daniil A. Andrienko; The importance of O3 excited potential energy surfaces in O2–O high-temperature kinetics. J. Chem. Phys. 31 January 2020; 152 (4): 044305. https://doi.org/10.1063/1.5142191
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