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Theoretical Studies on the Dynamics of Photochemical Processes in Solutions

Research Project

Project/Area Number 03453008
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KATO Shigeki  Kyoto Univ., Science, Professor, 理学部, 教授 (20113425)

Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1992: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1991: ¥5,400,000 (Direct Cost: ¥5,400,000)
KeywordsSolution Phase Reaction / Photochemical Processes / Molecular Theory / Electron Transfer / Norrish type II Reaction / Molecular Dynamics / Free Energy Surface / Norrish typeII反応 / 溶液 / 電子移動反応 / Norrish typeII / ジラジカル / 分子軌道法
Research Abstract

This research started in 1991 with the aim to provide realistic molecular models for the dynamics of photochemical processes in solutions. We have carried out the molecular dynamics (MD) calculations for the Norrish type II reaction and the photo-induced charge transfer state formation reaction of 4-(N,N-dimethylamino)benzonitrile(DMABN). For the Norrish type II reaction, the mechanism of electronic relaxation of 1,4-diradical intermediate derived from butanal was examined. The ab initio calculations were performed to obtaine the potential energy surfaces of singlet and triplet diradicals and the spin-orbit coupling element between them. The MD calculations for the diradical in methanol solution were carried out to obtain the rate constant for the triplet-singlet transition. The results were consistent with the experimental findings. For the photo-induced electron transfer reaction of DMABN, we derived a new reaction surface Hamiltonian for the torsional mode of dimethylamino group and the solvation coordinate by assuming the harmonic bath model for the solvent motions. The MD calculations were utilized to obtain various quantities included in the Hamiltonian such as the free energy surface, the effective mass for the solvation coordinate and the friction kernel for the solvent relaxation. The stochastic trajectory calculations were carried out to obtain the reaction rate.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] S.Ten-no: "RISM-SCF Study for Solvation Effect on Carbonyl Compounds in Aqueous Solution." J.Chem.Phys.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Sato: "Potential Surfaces of Chemical Reactions in Solution by Dielectric Continuum Method." J.Mol.Strucc.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Arai: "Ab Initio Potential Surfaces for theO('D)+Methane Reaction" J.Phys,chem.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Katagiri: "The Spin-Orbit Effect on Potential Surfaces of NO_2 Photodissociation" J.Chem.Phys.99. 8805-8815 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] S.Ten-no: "A Hybrid Approach for the Solvent Effect on the Electronic Strtcture of a Solute Based on the RISM and Hartree-Fock Equations" Chem.Phys.Lett.214. 391-396 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Morita: "Theoretical Study on the Intersystem Crossing Mechanism of a Diradical in Norrish Type II Reactions in Solution" J.Phys.Chem.97. 3298-3313 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Morita: "Theoretical Study on the Intersystem Crossing Mechanism of a Diradical in Norrish Type II Reactions in Solution" J.Phys.Chem.97. 3298-3313 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] S.Ten-no: "A Hybrid Approach for the Solvent Effect on the electronic Structure of a Solute Based on the RISM and Hartree-Fock Equations" Chem.Phys.Lett.214. 391-396 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Katagiri: "The Spin-Orbit Effect on Potential Surfaces of NO_2 Photodissociation" J.Chem.Phys.99. 8805-8815 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Arai: "Ab Initio Potential Surfaces for the O(^1D)+ Methane Reaction" J.Phys.Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Sato: "Potential Surfaces of Chemical Reactions in Solution by Dielectric Continuum Method." J.Mol.Strucc.(Theo.Chem.). (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] S.Ten-no: "RISM-SCF Study for Solvation Effect on Carbonyl Compounds in Aqueous Solution." J.Chem.Phys.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Morita: "Potential Energy Surfaces and the Spin-Orbit Coupling for H_20_2 Photodissociation" J.Phys.Chem.96. 1067-1073 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Sato: "Theoretical Study on the Interaction between a Meta Chelete and a Clay:Monte Carlo Simulation" J.Phys.Chem.96. 9377-9382 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Sato: "Theoretical Studies on Recemic Adsorption of Tris(1,10-phenanthroline)metal(II) by a Clay:Monte Carlo Simulations" J.Phys.Chem.96. 9382-9387 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Sato: "Monte Carlo Simulations for the Interactions of Metal Complex with the Silicate Sheets" J.Amer.Chem.Soc.114. 10933-10940 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] A.Morita: "Theoretical Study on the Intersystem Crossing Mechanism of a Diradical in Norrish Type II Reactions in Solution" J.Phys.Chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] 安藤 耕司: "Dielectric Relaxation Dynamics of Water and Methanol Solutions Associated with the Ionization of N,Nーdimethylaniline:Theoretical Analyses" Journal of Chemical Physics. 95. 5966-5982 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 森田 明宏: "Potential Energy Surfaces and the SpinーOrbit Coupling for H_2O_2 Photodissociation:The Importance of the Intersystem Crossing for ーtype Polarization of OH" Jounal of Physical Chemistry. 96. 1067-1073 (1992)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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