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Theoretical Study on Chemical Reaction Transition State

Research Project

Project/Area Number 04044193
Research Category

Grant-in-Aid for Overseas Scientific Survey.

Allocation TypeSingle-year Grants
Research InstitutionOkazaki National Research Institutes

Principal Investigator

MOROKUMA Keiji  Okazaki National Research Institutes , Institute for Molecular Science, 分子科学研究所, 教授 (40111083)

Co-Investigator(Kenkyū-buntansha) DIDIEU Alain  Universite Louis Pasteur, パスツール大学・量子化学研究室, 室長
LEFORESTIER Claude  Universite de Paris-Sud, 理論化学研究室, 教授
KOGA Nobuaki  Okazaki National Research Institutes, Institute for Molecular Science, 分子科学研究所, 助手 (80186650)
YAMASHITA Koichi  Institute for Fundamental Chemistry, 主任研究員 (40175659)
Project Period (FY) 1992
Project Status Completed (Fiscal Year 1992)
KeywordsComplex coordinate method / Discrete variable representation / Resonance scattering states / Transition state spectroscopy / oxo complex / Hydroxylation / Ab initio molecular orbital method / Theoretical chemistry
Research Abstract

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

Report

(1 results)
  • 1992 Final Research Report Summary
  • Research Products

    (4 results)

All Other

All Publications (4 results)

  • [Publications] 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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] C.Leforestier: "A Complex Discrete Variable Representation Method:Application to the transition State Spectroscopy in C1HC1-Photodetachment"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] C. Leforestier: "A Complex Discrete Variable Representation Method : Application to the Transition State Spectroscopy in ClHCl^- Photodetachment"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary

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Published: 1994-03-24   Modified: 2016-04-21  

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