| Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone |
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| 引用本文： | Fang Decai and Fu Xiaoyuan (Department of Chemistry,Beijing Normal University,Beijing). Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone[J]. 高等学校化学研究, 1990, 0(1) |
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| 作者姓名： | Fang Decai and Fu Xiaoyuan (Department of Chemistry Beijing Normal University Beijing) |
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| 作者单位： | Department of Chemistry，Beijing Normal University，Beijing |
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| 摘 要： | The mechanism of photocycloaddition reaction between 6-azauracll and acetone was studied by using semiemptrical SCFMO AMI method. It was found that this reaction is not a concerted one. The calculated results are as follows:(1) A T1 state exciplex is on the T1 state energy surface; (2) T exciplex as a reactant will proceed along the energy surface of T1 state to form a diradical intermediate. The energy barrier of this reaction step is 63. 6 kJ/mol; (3) The T1 state diradical intermediate happens to be close in energy to the ground state intermediate with a similar geometry. Such a situation turns out to be very favorable for an intersystem crossing (jump from the T, state to the ground state) ; (4) The final product will be formed from the ground S0 state intermediate via an energy barrier 88. 2 kJ/mol.
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Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone |
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| Fang Decai and Fu Xiaoyuan. Theoretical Studies on the Mechanism of Photocycloaddition Reaction Between 6 Azauracil and Acetone[J]. Chemical Research in Chinese University, 1990, 0(1) |
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| Authors: | Fang Decai and Fu Xiaoyuan |
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| Abstract: | The mechanism of photocycloaddition reaction between 6-azauracll and acetone was studied by using semiemptrical SCFMO AMI method. It was found that this reaction is not a concerted one. The calculated results are as follows:(1) A T1 state exciplex is on the T1 state energy surface; (2) T exciplex as a reactant will proceed along the energy surface of T1 state to form a diradical intermediate. The energy barrier of this reaction step is 63. 6 kJ/mol; (3) The T1 state diradical intermediate happens to be close in energy to the ground state intermediate with a similar geometry. Such a situation turns out to be very favorable for an intersystem crossing (jump from the T, state to the ground state) ; (4) The final product will be formed from the ground S0 state intermediate via an energy barrier 88. 2 kJ/mol. |
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| Keywords: | 6-Azauracil Acetone Diradical intermediate the T1 state The mechanism of photocycloadditlon reaction Intersystem crossing. |
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