Theoretical Study on Chemical Reaction Transition State

化学反应过渡态的理论研究

• 批准号: 04044193
• 负责人: MOROKUMA Keiji
• 金额: --
• 依托单位: Okazaki National Research Institutes
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Overseas Scientific Survey.
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04044193/
• 关键词: Complex coordinate method; Discrete variable representation; Resonance scattering states; Transition state spectroscopy; oxo complex; Hydroxylation; Ab initio molecular orbital method; Theoretical chemistry

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

我们已经对两个有趣领域的过渡状态的电子和几何结构进行了理论研究：气相中的反应和过渡金属复合物的反应。Neumark等人的光检查实验。为观察双分子化学反应的过渡状态区域观察共振散射状态提供了绝佳的机会。我们开发了一种使用复杂坐标方法的DVR公式来研究共振散射状态的新方法。共振位置和宽度取决于复杂缩放的哈密顿矩阵的复杂特征值。该方法应用于CLHCL阴离子的光检查光谱。通过Hypersphere坐标系统得出了程序代码。在CLHL中性分离过程的情况下，超晶体坐标系统的径向分量几乎对应于反应路径。 LEPS势能函数使用…更多d。沿着径向坐标，表面状态（振动绝热的势能曲线）表明，在约5000和7000 cm^ - 的能量下发现了两个可以支持共振散射状态的井。我们通过将径向坐标旋转到复杂平面，将复杂的DVR方法应用于系统的较低共振态。共振状态位于共振位置5189.8 cm^ - ，宽度为16.9 cm^<-1>。结果与标准l^2变异方法获得的结果非常吻合。均质催化剂对碳氢化合物的氧化是具有较强当前利益的对象。在该领域取得的最新进展中，发现使用氢过氧化物（例如T-BuOOH）与第10组过渡金属配合物（Ni，Pd，Pt）的使用。根据Van Koten等人的实验。我们研究了Ab Inli算分子轨道方法模型反应PD（CH_3）_2（NH_3）_2+H_2O_2，以评估PD = O oxo中间体的可能存在，并且是否可以确定其结构，并确定其与PD（II）相互作用的其他结构是否也参与了ROOH的相互作用。在相关的MP2水平上计算出导致PD（O）（CH_3）_2（NH_3）_2+H_2O的反应仅为2 KaCl/mol吸热，这表明Oxo复合物可以DE中间体。较少的

项目成果

C.Leforestier: "A Complex Discrete Variable Representation Method:Application to the transition State Spectroscopy in C1HC1-Photodetachment"

C.Leforestier：“一种复杂的离散变量表示方法：在 C1HC1-光分离中过渡态光谱的应用”

K.Yamashita: "New Ab Initio Potential Enerqy Surfaces and Three-Dimensional Quantum Dynamics for Transition State Soectroscopy in Ozone Photodissociation" Chem.Phys.Lett.191. 515-520 (1992)

K.Yamashita：“臭氧光解离中过渡态光谱的新从头计算势能面和三维量子动力学”Chem.Phys.Lett.191。

K. Yamashita: "New Ab Initio Potential Energy Surfaces and Three-Dimensional Quantum Dynamics for Transition State Spectroscopy in Ozone Photodissociatio" Chem. Phys. Lett.191. 515-520 (1992)

K. Yamashita：“臭氧光解离过渡态光谱的新从头算势能面和三维量子动力学” Chem。