Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University , Atlanta, Georgia 30322, United States.
J Phys Chem A. 2013 Nov 21;117(46):11665-72. doi: 10.1021/jp312076z. Epub 2013 Feb 1.
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. and Lin, M. C. Chem. Phys. Lett. 2009, 478, 11].
我们报道了基于拟合大约 114000 个密度泛函理论（UB3LYP/6-311+g(d,p)）电子能的 CH3NO2 的全局势能面（PES）。该 PES 是对这些能量的精确、置换不变拟合。描述了 PES 的性质，并进行了一些初步的准经典轨迹计算。发现了一条向 CH3ONO 异构体然后向 CH3O + NO 产物的异构化漫游途径。尽管该途径发生在比 PES 上相关的松弛鞍点更大的距离处，但该途径支持了基于定位松弛的一阶鞍点和相关 IRC 的假设，朱和林先前曾报道过 [Zhu, R. S. and Lin, M. C. Chem. Phys. Lett. 2009, 478, 11]。
