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Theoretical Study on Chemical Reaction Transition State

化学反应过渡态的理论研究

基本信息

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

项目摘要

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

我们在气相反应和过渡金属配合物反应两个有趣的领域对过渡态的电子结构和几何结构进行了理论研究，Neumark等人的光剥离实验为观察双分子化学反应过渡态区的共振散射态提供了极好的机会。我们发展了一种新的方法来研究共振散射态使用DVR制定的复坐标方法。共振位置和宽度由复尺度哈密顿矩阵的复特征值确定。该方法被应用到光剥离光谱的ClHCl阴离子。在超球坐标系下编制了程序代码。对于ClHl中性解离过程，超球坐标系的径向分量与反应路径基本一致，采用LEPS势能函数 ...更多信息 D.沿着径向坐标，表面态（振动绝热势能曲线）表明，在5000和7000 cm^-附近发现了两个支持共振散射态的威尔斯阱。通过将径向坐标旋转到复平面，将复DVR方法应用于系统的低共振状态。共振态位于共振位置5189.8cm ^-和宽度16.9cm ^-处<-1>。计算结果与标准L^2变分法所得结果一致。均相催化剂催化烃类氧化反应是当前研究的热点之一。在该领域取得的最新进展中，发现了氢过氧化物如t-BuOOh与第10族过渡金属络合物（Ni、Pd、Pt）的用途。根据货车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，以评估Pd=O氧代中间体的可能存在，如果存在，确定其结构，并检查是否还涉及由ROOH与Pd（II）配合物相互作用产生的其他结构。在MP2水平上计算了生成Pd（O）（CH_3）_2（NH_3）_2+H_2O的反应为2kacl/mol吸热反应，表明该氧代配合物可以生成中间体。少