Electronic Structures of Ions of m-Phenylenebis (Phenylmethylene).II:The Electron Correlation Effects

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概要

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• m-Phenylenebis (phenylrnethylene) (rn-PBPVI) has the quintet ground state in the netrtralstate, due to the dynaznic spin polarization (DSP) in the 7 system and exchange interactionbetween n and m electrons on carbenes. The experiznental restrlts by the ESR shoxv that bothnaonocation and unonoanion of' m-PBPIVI have the qu?rrtet ground state. We caIctr[ate the e[ec-tronic strtrctures of the ions with the unrestricted Hartree-Fock (UHF) and resonating HartreeFock (Res IF) methods. We trse the model that includes only n and 7T electrons developed in apICVl0LlS paper. The broken spatial zrnd spin syrnametries of the UHF solutions are restored bythe Res HF calcttlations of electron correlartion eff'ects. In the UHF approximation, the dopedcharge is alxvays localized on a carbene and the ad.jacent phenylenes as a spin density wave(SDW) po[aron. The II spins Qll the right and left carbenes are parallel and antiparaIIe[ irr theqtuartet and doulclet states, respectively. Dvre to this fact, the stabilization by the quantumnaotion of the SDW P0J2lIOIl betxveen the two carlcenes is l;xrger in the qvtartet state than in tiredoublet state by about 0.18 eV in the Res HF calculations with the UHF solutions used as atrial bases. Apart from such stabilization, qu?tnttruaa flucttnations of the charge and spin in thephenylenes are significant. In the Res HF calctrlations with many bases to treat the fluctuations,the stabilization energies are about 2 eV irt both the quartet and dotrblet states that are abotrtthree titnes of the ground state correlation energy in benzene. Therefore, when the electroncorrelations are considered enough, the quartet states are more stable than the dotrlcJet statesby 0.12 eV in the cation and 0.15 eV in the anion, respectively. These energy gaps are broughtabout by the quantuna naotion of' the SDW pot;tron ]*etween the two carbenes.

• 社団法人日本物理学会の論文
• 1997-03-15

著者

• Fukutome Hideo

  Depatment Of Physics Kyoto University

• MIZOUCHI Hideo

  Depatment of Physics,Kyoto University

• IKAWA Atsushi

  Depatment of Physics,Kyoto University

• Ikawa Atsushi

  Depatment Of Physics Kyoto University

• Mizouchi Hideo

  Depatment Of Physics Kyoto University

関連論文

• Electronic Structures of Ions of m-Phenylenebis (Phenylmethylene).II:The Electron Correlation Effects
• Electronic Structures of Ions of m-Phenylenebis (Phenylmethylene).I:UHF Studies
• A Semi-Empirical Model Study of the Electronic and Lattice Structure of a Pressure-Quenched Se-Te Mixed Crystal

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