高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (2): 284.

• 论文 • 上一篇    下一篇

ClONO2及其异构体光解反应的从头算研究(Ⅱ)——ClONO2→ClO+NO2反应机理研究

林梦海1, 林连堂1, CHIU CHOW Lue-Yung2   

  1. 1. 厦门大学化学系, 物理化学研究所, 厦门, 361005;
    2. Howard大学化学系, 华盛顿特区, 20059, 美国
  • 收稿日期:1996-11-01 出版日期:1998-02-24 发布日期:1998-02-24
  • 通讯作者: 林梦海,联系人:女,51岁.硕士,副教授.
  • 作者简介:林梦海,女,51岁.硕士,副教授.
  • 基金资助:

    国家自然科学基金资助课题.

Ab Initio Study on Photolysis of Chlorine Nitrate and Its Isomers(Ⅱ)——Investigation of Reaction Mechanism of ClONO2→ClO+NO2

LIN Meng-Hai1, LIN Lian-Tang1, CHIU CHOW Lue-Yung2   

  1. 1. Department of Chemistry and Institute of Physical Chemistry, Xiamen University, Xiamen, 361005;
    2. Department of Chemistry, Howard University, Washington D.C. 20059, U.S.A.
  • Received:1996-11-01 Online:1998-02-24 Published:1998-02-24

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摘要： 用从头算方法讨论了大气臭氧层主要破坏物ClONO2在光照下分解反应途径:ClONO2→ClO+NO2的反应机理.该反应的2个过渡态ClO…NOO(TS2a)和OCI…NOO(TS2b)中TS2a能垒较高,始态难于越过如此高的势垒;TS2b势垒较低,而产物到过渡态TS2b的能垒也仅有1.20 eV,故预测该反应为一个可逆反应.

关键词: 氯硝酸根, ClONO2, 光解反应, 反应机理, 从头算

Abstract: The reaction mechanism of photolysis for chlorine nitrate that causes ozone lost in the stratosphere ClONO2→ClO+NO2 has been studied by using ab initio calculation method. Two transition states TS2a and TS2b have been found, but it is difficult to overcome so high energy barrier to get to TS2a, and it is easy to pass TS2b over 4.20～4.35 eV energy barrier from the initial state(conformation (B) or (D)) to the final state. However only 1.20 eV is required to pass TS2b from ClO+NO2 to ClONO2, so reaction path (2) is a reversible reaction.

Key words: Chlorine nitrate, ClONO2, Photolysis reaction, Reaction mechanism, Ab initio

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