Quasiclassical Trajectory Study of CH sub(3)NO sub(2) 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 Vol. 117; no. 46; pp. 11665 - 11672-11665-11672
• Main Authors: Homayoon, Zahra, Bowman, Joel M
• Format: Journal Article
• Language: English
• Published: 01-01-2013
• Subjects: Density functional theory; Invariants; Isomerization; Isomers; Mathematical analysis; Pathways; Potential energy; Trajectories
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp312076z

We report a global potential energy surface (PES) for CH sub(3)NO sub(2) 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 CH sub(3)ONO isomer and then to the CH sub(3)O + 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. and Lin, M. C. Chem. Phys. Lett. 2009, 478, 11].