Global Potential Energy Surfaces by Compressed-State Multistate Pair-Density Functional Theory for Hyperthermal Collisions in the O2 + O2 System

Chemphyschem. 2024 Mar 25:e202400078. doi: 10.1002/cphc.202400078. Online ahead of print.ABSTRACTInteractions 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 O4 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 + O3 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 O2-O2 collisions.PMID:38526528 | DOI:10.1002/cphc.202400078

Source: Chemphyschem - March 25, 2024 Category: Chemistry Authors: Jie Jiang Jiawei Yang Qizhen Hong Quanhua Sun Jun Li Source Type: research