Li Y Q, Zhang P Y, Han K L
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Chem Phys. 2015 Mar 28;142(12):124302. doi: 10.1063/1.4916035.
A global many-body expansion potential energy surface is reported for the electronic ground state of CH2 (+) by fitting high level ab initio energies calculated at the multireference configuration interaction level with the aug-cc-pV6Z basis set. The topographical features of the new global potential energy surface are examined in detail and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. In turn, in order to validate the potential energy surface, a test theoretical study of the reaction CH(+)(X(1)Σ(+))+H((2)S)→C(+)((2)P)+H2(X(1)Σg (+)) has been carried out with the method of time dependent wavepacket on the title potential energy surface. The total integral cross sections and the rate coefficients have been calculated; the results determined that the new potential energy surface can both be recommended for dynamics studies of any type and as building blocks for constructing the potential energy surfaces of larger C(+)/H containing systems.
通过拟合在多参考组态相互作用水平下使用aug-cc-pV6Z基组计算得到的高水平从头算能量，报道了CH2(+)电子基态的全局多体展开势能面。详细研究了新全局势能面的地形特征，发现与直接从原始从头算能量计算得到的结果以及文献中先前的计算结果吻合良好。反过来，为了验证该势能面，在标题势能面上采用含时波包方法对反应CH(+)(X(1)Σ(+))+H((2)S)→C(+)((2)P)+H2(X(1)Σg (+))进行了理论测试研究。计算了总积分截面和速率系数；结果表明，新势能面既适用于任何类型的动力学研究，也可作为构建更大含C(+)/H体系势能面的基础。
