State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Chem Phys. 2011 Sep 14;135(10):104314. doi: 10.1063/1.3636113.
A new global potential energy surface is reported for the ground state ((4)A(")) of the reaction H((2)S) + NH(X(3)Σ(-)) → N((4)S) + H(2) from a set of accurate ab initio data, which were computed using the multi-reference configuration interaction with a basis set of aug-cc-pV5Z. The many-body expansion and neural network methods have been used to construct the new potential energy surface. The topographical features of the new global potential energy surface are presented. The predicted barrier height is lower than previous theoretical estimates and the heat of reaction with zero-point energy is closer to experimental results. The quantum reactive scattering dynamics calculation was carried out over a range of collision energies (0-1.0 eV) on the new potential energy surface. The reaction probabilities, integral cross-section, and rate constants for the title reaction were calculated. The calculated rate constants are in excellent agreement with the available experimental results.
报道了一个新的用于基态((4)A("))反应 H((2)S) + NH(X(3)Σ(-)) → N((4)S) + H(2)的全球势能面，该势能面是基于多参考组态相互作用方法和 aug-cc-pV5Z 基组计算得到的高精度从头算数据。使用多体展开和神经网络方法构建了新的势能面。呈现了新的全球势能面的地形特征。预测的势垒高度低于先前的理论估计，并且零能反应热更接近实验结果。在新势能面上进行了一系列碰撞能量(0-1.0 eV)的量子反应散射动力学计算。计算了标题反应的反应概率、积分截面和速率常数。计算得到的速率常数与现有的实验结果非常吻合。
