• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

1994 Fiscal Year Final Research Report Summary

DEVELOPMENT OF MOLECULAR THEORY FOR THE CALCULATION OF POTENTIAL ENEGY SURFACES

Research Project

Project/Area Number 05453019
Research Category

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

Allocation TypeSingle-year Grants
Research Field Physical chemistry
Research InstitutionTHE UNIVERSITY OF TOKYO

Principal Investigator

HIRAO Kimihiko  The UNIVERSITY OF TOKYO,FACULTY OF engineering, PROFESSOR, 工学部, 教授 (70093169)

Project Period (FY) 1993 – 1994
KeywordsMRMP THEORY / MULTIREFERENCE PERTURBATION THEORY / MOLECULAR ELECTRONIC THEORY / CORRELATION PROBLEM / POTENTIAL ENERGY SURFACES / EXCITED STATES
Research Abstract

Single reference perturbation theory and cluster expansion theory such as symmetry adapted cluster and coupled cluster theories are very effective in describing dynamical correlation but fail badly in dealing with nondynamical correlation. CI is easily applied in multireference form and can handle nondynamical correlation but the CI expansion becomes less compact and less efficient as the number of electrons in the system grows. Therefore we have developed multireference based Rayleigh-Schrodinger perturbation theory. The MRMP is reliable and retains the attractive features of the single reference MP method. The theory has conceptual simplicity due to the independent electron pair model. It is almost size consistent. It is very efficient and cost effective. Multireference technique can dissociate a molecule correctly into its fragments. It is applicable to open shells and excited states.
The state-specific MRMP has been sucessfully applied to the calculations of the potential energy surfaces of chemical reactions. Also the theory was applied to the study of valence and Rydberg excitation energies of benzene. The results compare well with the experiment. The calculated valence pi-pi^* excitation energies (experimental values in parentheses) are ^1B_<2u>,4.77 (4.90), ^1B_<1u>,6.28 (6.20), ^1E_<1u>,6.98 (6.94) and ^1E_<2g>,7.88 (7.80) eV,respectively. The Rydberg excitation energies are also predicted with an accuracy of 0.18 eV or better. Results of similar accuracy are obtained for the valence and Rydberg excitation energies for cyclopentadiene, furan, pyrrole, naphthalene and ozone.

  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] K.Hirao: "State-specific multireference Moller-Plesset perturbation treatment for singlet and triplet excited states,ionized states and electron attached states of H_2O" Chem Phys.Lett.201. 59-66 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yamamoto: "Molecular applications of the generalized symmetry adaped cluster theory" Chem,Phys.Lett.204. 315-319 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Obata: "Structure and Vibrational Analysis of Protonated Ethane C2H7+" Bull.Chem.Soc.Japan. 66. 3271-3282 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Obara: "Molecular.Integrals in the Equation of Correlated Electronic Wave Function Including Interparticle Distances" Bull.Chem.Soc.Japan. 66. 3300-3308 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Hirao: "Calculation of potential energy sarfaces for Chemical reactions" New Functionality Materials,Vol.C23GE05:1993. 63-68

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Yamanaka: "CASPT2 and MRMP2 calculations of potential curves and effective exchange integrals for the dimer of triplet methylene" Chem.Phys.Lett.225. 213-220 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Hirao: "Multireference Moller-Plesset Perturbation Treatment for Valence and Rydbery Excited States of Benzene" Chem.Phys.Lett.(発表予定).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Hirao: "Recent Development of Electronic Stracture Theory" Functionality of Molecular Systems. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hashimoto: "Is CrF6 Octahedral? MRMP theory and DFT also confirm “Yes!"" Inorganic Chemistry. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Nakano: "Multireference Moller-Plesset Perturbation Treatment for Excited States of Ciyclopentadieve,Pyrrole and Furan" Chem.Phys.Lett.(発表予定).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Mogi: "Diabatic and adia bafic Lagrange-Newton methods to determine the basic characteristic of potential energy surfaces in the state-to-state reactions" J.Phys.Chem.(発表予定).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Hirao: "State-specific multireference Moller-Plessetperturbation theatment for singlet and triplet excited states, ionized states and electron attached states of H20" Chem.Phys.Lett.201. 59-66 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] "Molecular application of the generalized symmetry adapted cluster theory" Chem.Phys.Lett.204. 315-319 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Obata: "Structure and Vibrational Analysis of Protonated Ethane C2H7+" Bull.Chem.Soc.Japan. 66. 3271-3282 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Obata: "Molecular Integrals in the Equation of Correlated Electronic Wave Function Including Interparticle Distances" Bull.Chem.Soc.Japan. 66. 3300-3308a (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Hirao: "Calculation of potential energy surfaces for chemical reactions" New Functionality Materials. Vol.C. 63-68 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Yamanaka: "CASPT2 and MRMP2 calculations of potenital curves and effective exchange integrals for the dimer of triplet methylene" Chem.Phys.Lett.225. 213-220 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Hirao: "Multireference Moller-Plesset Perturbation Theatment for Valence and Rydberg Excited States of Benzene" Chem.Phys.Lett.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Hirao: "Recent Development of Electronic Structure Theory" Functionality of Molecular Systems. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hashimoto: "Is CrF6 Octahedral? MRMP theory and DFT also confirm "Yes! "" Inorganic Chemistry. (to be published).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Nakano: "Multireference Moller-Plesset Perturbation Treatment for Excited States of Cyclopendadiene, Pyrolle and Furan" Chem Phys Lett. (to be published).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Mogi: "Diabatic and adiabatic Lagrarange-Newton methods to determine the basic characteristic of potential energy surfaces in the state-to-state reactions" J.phys Chem. (to be published).

    • Description
      「研究成果報告書概要(欧文)」より

URL: 

Published: 1996-04-15  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi