Quasiclassical Trajectory Study of CH3NO2 Decomposition via Roaming Mediated Isomerization Using a Global Potential Energy Surface

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-11, Vol.117 (46), p.11665-11672
• Main Authors: Homayoon, Zahra, Bowman, Joel M
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Density-functional theory; Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Physics
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp312076z

We report a global potential energy surface (PES) for CH3NO2 based on fitting roughly 114 000 density functional theory (UB3LYP/6-311+g(d,p)) electronic energies. The PES is a precise, permutationally invariant fit to these energies. Properties of the PES are described, as are some preliminary quasiclassical trajectory calculations. An isomerization-roaming pathway to the CH3ONO isomer and then to the CH3O + NO products is found. Although the pathway occurs at larger distances than a related loose saddle-point on the PES, the pathway supports the supposition of such a pathway based on locating a loose first-order saddle point and associated IRC, reported previously by Zhu and Lin [ Zhu R. S. ; Lin M. C. Chem. Phys. Lett. 2009, 478, 11 ].