Quantum dynamics studies of chemical reactions

我们从头开始计算了电子与H_3^+的解离附著过程、H_2CO的单分子反应以及NOCI在紫外区的光解离动力学。我们开发了一个有效的哈密顿量来描述H_3里德伯态的量子动力学和导致解离通道的高激发里德伯态的弛豫动力学。构造了能描述H_2CO分子解离和异构化通道的全局势能函数，并利用沃森哈密顿量计算了这些通道的累积反应概率。设计了一种处理振动角动量项的有效算法。对于NOCI，基于MRCI计算构建了7个态的解析势函数，并进行了量子动力学计算，获得了基态表面的电子谱和拉曼谱以及振动态的完整列表。我们还研究了A带区域的光解离动力学，并以一致的方式解释了许多实验结果。

We carried out ab initio electronic structure and quantum dynamics calculations for the dissociative attachment process of electron to H_3^+, unimolecular reactions of H_2CO, and photo-dissociation dynamics of NOCI in the UV region. We developed an effective Hamiltonian for describing the quantum dynamics of H_3 Rydberg states and the relaxation dynamics of highly excited Rydberg Etatesleading to the dissociation channel swasexamined.A global potential energy function of H_2CO, which can describe both the molecular dissociative and isomerization channels, was constructed and the cumulative reaction probabilities of these channels were calculated with using the Watson Hamiltonian. An efficient algorithm was devised to treat the vibrational angular momentum term. For NOCI, analytical potential functions for seven states were constructed based on MRCI calculations and the quantum dynamics calculations were carried out to obtain the electronic and Raman spectral profiles as well as a full list of vibrational states on the ground state surface. We also examined the photo-dissociation dynamics at A band region and explain many experimental findings in a consistent way.