Theoretical Study on Chemical Reaction Transition State

我们在两个有趣的领域：气相反应和过渡金属络合物的反应中，对过渡态的电子结构和几何结构进行了理论研究。为观察双分子化学反应过渡态区域的共振散射态提供了一个很好的机会。我们发展了一种利用复坐标法的DVR公式来研究共振散射态的新方法。共振位置和宽度由复尺度哈密顿矩阵的复本征值确定。将该方法应用于ClHCl阴离子的光解离光谱。程序代码是在超球坐标系下开发的。在ClHl中性解离过程中，超球坐标系的径向分量几乎对应于反应路径。LEPS势能函数采用…沿径向坐标的表面态(振动绝热势能曲线)表明，在5000和7000 cm^-能量附近发现了两个能支持共振散射态的势垒。通过将径向坐标旋转到复平面，我们将复数DVR方法应用于系统的低谐振态。共振态位于5189.8 cm^-，宽度为16.9 cm^-1&gt；所得结果与标准的L^2变分方法得到的结果吻合较好。均相催化剂氧化碳氢化合物是当前研究的热点问题。在这一领域取得的最新进展中，ON发现了过氧化氢的用途，如t-BuOOH与第10族过渡金属络合物(Ni、Pd、Pt)的使用。根据van Koten等人的实验。我们用从头算分子轨道方法研究了模型反应Pd(CH_3)_2(NH_3)_2H_2O_2，以评估Pd=O氧中间体的可能存在，如果存在，确定其结构，并检查是否也涉及RoOH与Pd(II)络合物相互作用产生的其他结构。在关联MP2水平上计算得到Pd(O)(CH3)2(NH3)2H2O的反应吸热系数仅为2kacl/mol，表明该氧配合物可分解为中间体。较少

We have carried out theoretical studies on the electronic and geometrical structure of a transition state in the two interesting fields : reactions in gas phase and those of transition metal complexes.The photodetachment experiment by Neumark et al. offers an excellent opportunity for the observation of resonance scattering states in the transition state region of bimolecular chemical reactions. We developed a new method to study the resonance scattering states using the DVR formulation of the complex coordinate method. The resonance positions and widths are determined from the complex eigenvalues of the complex scaled Hamiltonian matrix. The method was applied to the photodetachment spectroscopy of the ClHCl anion. The program code has been developed fro the hyperspherical coordinates system. In the case of ClHl neutral dissociation process, the radial component of the hyperspherical coordinates system nearly corresponds to the reaction path. The LEPS potential energy function was use … More d. Along radial coordinate, the surface states (vibrationally adiabatic potential energy curves) show that two wells which can support resonance scattering states have been found at the energy of around 5000 and 7000 cm^-. We applied the complex DVR method to the lower resonance state of the system by rotating the radial coordinates to the complex plane. A resonance state has been located at the resonance position of 5189.8 cm^- and the width of 16.9 cm^<-1>. The results are in good agreement with the ones obtained by a standard L^2 variational method.The oxidation of hydrocarbons by homogeneous catalyst is a subject of strong current interest. Among the recent advances made in this field, on finds the use of hydroperoxides such as t-BuOOh with group 10 transition metal complexes (Ni, Pd, Pt). According to the experiments by van Koten et al. we studied with ab initio molecular orbital method the model reaction, Pd(CH_3)_2(NH_3)_2+H_2O_2, in order to assess the possible existence of a Pd=O oxo intermediate and if so, to determine its structure, and to check whether other structures resulting from the interaction of ROOH with the Pd(II) complex might be also involved. The reaction leading to Pd(O)(CH_3)_2(NH_3)_2+H_2O was calculated at the correlated MP2 level to be only 2 kacl/mol endothermic, showing that the oxo complex could de an intermediate. Less