Accurate ab initio based potential energy surface and kinetics of the Cl + NH3 → HCl + NH2 reaction

• DOI: 10.1063/5.0216562
• Publication Date: 2024-07-15T10:18:38Z
• Authors: Zhao Tu; Jiaqi Li; Mingjuan Yang; Yizhuo Chen; Yan Wang; Hongwei Song
• Keywords: Potential energy surface; Hydrogen atom abstraction; Zero-point energy

The gas-phase reaction Cl + NH3 → HCl NH2 is a prototypical hydrogen abstraction reaction, whose minimum energy path involves several intermediate complexes. In this work, full-dimensional, spin–orbit corrected potential surface (SOC PES) constructed for the ground electronic state of reaction. About 52 000 points are sampled and calculated at UCCSD(T)-F12a/aug-cc-pVTZ level, in which data located entrance channel corrected. corrections predicted by fitted three-dimensional from about 7520 level CASSCF (15e, 11o)/aug-cc-pVTZ. fundamental-invariant neural network method utilized to fit SOC PES, resulting total root mean square error 0.12 kcal mol−1. thermal rate constants on PES with soft-zero-point constraint agree reasonably well available experimental values.