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

我们对两个有趣领域中过渡态的电子和几何结构进行了理论研究：气相反应和过渡金属配合物反应。Neumark等人的光脱离实验为观察共振提供了绝佳的机会。我们开发了一种使用复数坐标方法的 DVR 公式来研究共振散射态的新方法，共振位置和宽度由复数缩放的复数特征值确定。哈密​​顿矩阵。该方法应用于 ClHCl 阴离子的光脱离光谱。该程序代码是根据 ClHl 中性解离过程开发的，超球坐标系的径向分量几乎对应于反应。沿径向坐标使用 LEPS 势能函数，表面状态（振动绝热势能曲线）显示两个我们在 5000 和 7000 cm^- 左右的能量处发现了可以支持共振散射态的井，我们通过将径向坐标旋转到复平面上，将复数 DVR 方法应用于系统的较低共振态。其共振位置为 5189.8 cm^-，宽度为 16.9 cm^<-1>，结果与标准 L^2 变分法得到的结果非常吻合。通过均相催化剂氧化碳氢化合物是当前该领域取得的重大进展之一，其中发现使用氢过氧化物，例如 t-BuOOh 与第 10 族过渡金属配合物（Ni、Pd、Pt）。 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)_2+H_2O_2,为了评估 Pd=O 氧代中间体是否可能存在，如果存在，则确定其结构，并检查 ROOH 与 Pd(II) 络合物相互作用所产生的其他结构是否也可能涉及导致的反应。经计算，在MP2水平下，Pd(O)(CH_3)_2(NH_3)_2+H_2O的吸热仅为2 kacl/mol，表明该氧配合物可以脱除中间体。

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。