Global Potential Energy Surfaces by Compressed-State Multistate Pair-Density Functional Theory for Hyperthermal Collisions in the O 2 +O 2 System
Interactions between oxygen molecules play an important role in atmospheric chemistry and hypersonic flow chemistry in atmospheric entries. Recently, high-quality ab initio potential energy surface (PES) of the quintet O was reported by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. 10543 config...
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Published in | Chemphyschem Vol. 25; no. 12; p. e202400078 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Germany
17.06.2024
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Online Access | Get full text |
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Summary: | Interactions between oxygen molecules play an important role in atmospheric chemistry and hypersonic flow chemistry in atmospheric entries. Recently, high-quality ab initio potential energy surface (PES) of the quintet O
was reported by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. 10543 configurations were sampled and calculated at the level of MS-CASPT2/maug-cc-pVTZ with scaled external correlation. The PES was fitted to a many-body (MB) form with the many-body part described by the permutationally invariant polynomial approach (MB-PIP). In this work, the PIP-Neural Network (PIP-NN) and MB-PIP-NN methods were used to refit the PES based on the same data by Paukku et al. Three PESs were compared. It was found that the performances differ significantly in the O+O
region as well as in the long-range region. Therefore, additional 1300 points were sampled, and the efficient compressed-state multistate pair-density functional theory (CMS-PDFT) was used to calculate the electronic structure of these 1300 points and 10543 points by Paukku et al. Then, a completely new quintet PES was fitted using the MB-PIP-NN method. Based on this PES, the quasi-classical trajectory (QCT) approach was used to reveal all possible reaction channels for hyperthermal O
-O
collisions. |
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ISSN: | 1439-4235 1439-7641 |
DOI: | 10.1002/cphc.202400078 |