THEORETICAL-STUDY ON PHOTOOXYGENATION OF LARGE POLYCYCLIC AROMATIC-HYDROCARBONS BY SEMIEMPIRICAL MOLECULAR-ORBITAL METHODS

被引：12

作者：

SAKAI, KI

OHSHIMA, S

UCHIDA, A

OONISHI, I

FUJISAWA, S

NAGASHIMA, U

机构：

[1] TOHO UNIV,FAC SCI,DEPT BIOMOLEC SCI,FUNABASHI,CHIBA 274,JAPAN

[2] TOHO UNIV,FAC SCI,DEPT CHEM,FUNABASHI,CHIBA 274,JAPAN

[3] OCHANOMIZU UNIV,FAC SCI,DEPT INFORMAT SCI,BUNKYOU KU,TOKYO 112,JAPAN

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 16期

关键词：

D O I：

10.1021/j100016a027

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The photooxygenation reaction of large polycyclic aromatic hydrocarbons (PAHs) composed of more than six benzene rings was investigated by using the semiempirical molecular orbital method. The optimization of the PAHs and their endo-peroxides revealed that oxygen attaches to a pair of carbon atoms which have the largest pi-electron density of the highest occupied molecular orbital. The structure of the endo-peroxide of tetrabenzo[de,hi,op,st]pentacene, determined experimentally, could be reproduced by the calculation. The heats of formation for the PAHs, endo-peroxides, and transition states were also calculated, and an energy correlation diagram of the reaction was obtained. The experimental results for the rate of photooxygenation were explained in terms of the energy difference between the initial and transition states in the profile.

引用

页码：5909 / 5913

页数：5

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