Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University , Atlanta, Georgia 30322, United States.
J Phys Chem A. 2014 Jan 23;118(3):545-53. doi: 10.1021/jp410935k. Epub 2014 Jan 14.
We report a global potential energy surface (PES) for the N((2)D) + H2O reaction based on fitting roughly 312 000 UCCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. Quasiclassical trajectory calculations of the N((2)D) + H2O(D2O) reaction with focus on the NH(D) + OH(D) exit channel are performed. An analysis of the internal-state distributions shows that the NH(D) fragment has more internal energy, both rotational and vibrational than the OH(D) fragment, in good agreement with experiment. This difference is traced to nonstatistical dynamics.
我们报道了一个基于拟合约 312000 个 UCCSD(T)-F12/aug-cc-pVTZ 电子能的 N((2)D) + H2O 反应的全局势能面 (PES)。该表面是使用具有莫尔斯型变量的置换不变基的线性最小二乘拟合。我们进行了聚焦于 NH(D) + OH(D)出口通道的 N((2)D) + H2O(D2O)反应的准经典轨迹计算。对内部态分布的分析表明，NH(D)片段比 OH(D)片段具有更多的内部能量，无论是转动还是振动，这与实验结果一致。这种差异可以追溯到非统计动力学。
