An accurate multi-channel multi-reference full-dimensional global potential energy surface for the lowest triplet state of H2O2
An accurate multi-channel multi-reference full-dimensional global potential energy surface for the lowest triplet state of H2O2
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H2O2 最低三重态的精确多通道多参考全维全局势能面
DOI：
10.1039/c6cp06232f
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Hua Guo
中科院分区：
文献类型：
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作者：
Jun Li;Richard Dawes;Hua Guo
H2O2体系的最低三重态具有多个反应通道，其中包括几个与H2燃烧有关的反应通道。为了准确地绘制出全局势能面，在包括所有重要渐近线在内的大构型空间中采样了~ 28000个几何形状，并在多参考构型相互作用（MRCI-F12）的显式相关版本的水平上计算了这些点上的电子能量。利用置换不变多项式-神经网络方法对从头算数据集进行拟合，构建了一个新的多通道全局势能曲面，得到的总均方根拟合误差仅为6.7 meV （0.15 kcal mol−1）。在新的MRCI势能面上计算了几种相关反应的各种动力学和动力学性质，并与已有的实验结果进行了比较。
The lowest triplet state of the H2O2 system features multiple reaction channels, including several relevant to the combustion of H2. To accurately map out the global potential energy surface, ∼28 000 geometries were sampled over a large configuration space including all important asymptotes, and electronic energies at these points were calculated at the level of the explicitly correlated version of the multi-reference configuration interaction (MRCI-F12) method. A new multi-channel global potential energy surface was constructed by fitting the ab initio data set using a permutation invariant polynomial-neural network method, resulting in a total root mean square fitting error of only 6.7 meV (0.15 kcal mol−1). Various kinetics and dynamical properties of several relevant reactions were calculated on the new MRCI potential energy surface, and compared with the available experimental results.