| 双光子协同光化学周环反应的选择规则 |
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| 引用本文： | 张先付.双光子协同光化学周环反应的选择规则[J].河北科技师范学院学报,2014(2):9-14. |
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| 作者姓名： | 张先付 |
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| 作者单位： | [1]河北科技师范学院化学工程学院,河北秦皇岛066600; [2]MPC技术公司,加拿大海明顿 L8S 3H4 |
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| 摘 要： | 从理论和实验两方面比较了双光子(频率)和相应的单光子(频率2)协同周环反应。二者常得到不同的产物,表明Woodward-Hoffman规则不适用于双光子反应。为解释这一差异,提出用线性多烯烃的HudsonKohler态而不是休克尔分子轨道作为反应中双光子激发产生的最低激发态。根据这一能态的轨道对称性,并利用前线轨道理论,给出了双光子周环反应的选择规则。
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| 关 键 词： | 光化学 双光子反应 周环反应 Woodward-Hoffman规则 |
Rules of Two-Photon Concerted Photochemical Pericyclic Reactions and Its Difference from Woodward-Hoffman Rules for One-Photon Cases |
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| ZHANG xian-fu.Rules of Two-Photon Concerted Photochemical Pericyclic Reactions and Its Difference from Woodward-Hoffman Rules for One-Photon Cases[J].Journal of Hebei Normal University of Science & Technology,2014(2):9-14. |
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| Authors: | ZHANG xian-fu |
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| Institution: | ZHANG xian-fu( 1 College of Chemical and Engineering, Hebei Normal University of Science ＆ Technology, Qinhuangdao Hebei,066600, China ;2 MPC Tech, Hamilton, ON, Canada LSS 3 H4) |
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| Abstract: | A two-photon（ with frequency） reaction（ TPR） is compared with its corresponding one photon（ with frequency 2） counterpart（ SPR） both experimentally and theoretically.TPR often yields different products from its SPR,suggesting Woodward-Hoffman Rules do not apply for TPR.To explain the difference,it is proposed that Hudson-Kohler state of polyenes（ HKSP）,rather than the state in Huckel molecular orbital theory,acts as the lowest-lying excited state for the two-photon absorption（ TPA） involved in TPR.The selection rules for pericyclic TPR are derived based on the symmetry of HKSP and frontier orbital theory. |
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| Keywords: | photochemistry two-photon reaction pericyclic reaction Woodward-Hoffman rules |
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