Global and Full-Dimensional Potential Energy Surfaces of the N₂ + O₂ Reaction for Hyperthermal Collisions

Abstract

The energy transfer, dissociations, and chemical reactions between O 2 and N 2 play an important role in the re-entry process of aircraft and many atmospheric, combustion, and plasma processes. Recently, Varga et al. (J. Chem. Phys., 2016, 144, 024310) developed a full-dimensional high-precision potential energy surface (PES) of the ground triplet electronic state for the O 2 and N 2 system based on ca. 55,000 data points, whose energies were calculated by multi-state complete-active-space second-order perturbation theory/minimally augmented correlation-consistent polarized valence triple-zeta electronic structure calculations plus dynamically scaled external correlation. The fitting function adopted the many-body expansion form with the four-body interactions fitted by the permutationally invariant polynomial in terms of bond-order functions of the six interatomic distances (MB-PIP). In this work, we refit the PES of the N 2 O 2 system by two methods based on the same data set that was used by Varga et al. The first uses the permutation invariant polynomial−neural network (PIP-NN) method to fit the entire energy of the 55,000 data points. In the second approach, the PIP-NN method is used to fit only the four-body interaction component, a similar treatment in the MB-PIP method, and the resulting PES is named MB-PIP-NN. Then, the performances of these new PESs and the MB-PIP PES are comprehensively and systematically compared, such as comparisons of various scans, properties of stationary points, and dynamics simulations. Possible improvements for the PES of N 2 O 2 are suggested. A more reliable PES of the system can be constructed in terms of data sampling range, electronic structure calculation level, and fitting method for high-temperature calculation and simulation in the future.

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

“…Recently, Tao et al fitted the PES of the N 2 + O 2 system using the MB-PIP-NN method, which was shown to have better performance than the PIP-NN method, especially in the high-energy region. [34] In addition, the CMS-PDFT method was extensively tested (see Section 3.1.2 for details) and was chosen as the electronic structure method. This CMS-PDFT dataset is fitted by the MB-PIP-NN method, and the corresponding PES is then employed in the QCT [35] calculations to reveal possible mechanisms in the collisions in O 2 + O 2 .…”