高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (11): 2027.

• 论文 • 上一篇    下一篇

HCO+NO2反应势能面的理论研究

孙扬, 孙延波, 黄旭日, 孙家锺   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2003-03-21 出版日期:2003-11-24 发布日期:2003-11-24
  • 通讯作者: 黄旭日(1962年出生),男,博士,教授,博士生导师,从事量子化学计算研究.E-mail:lhs@mail.jlu.edu.cn E-mail:lhs@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29892168;20073014);教育部博士学科点基金;教育部骨干教师基金;吉林大学青年教师基金;吉林省科技发展基金资助

Theoretical Studies on Reaction Potential Energy Surface of the Formyl Radical with Nitrogen Dioxide

SUN Yang, SUN Yan-Bo, HUANG Xu-Ri, SUN Chia-Chung   

  1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China
  • Received:2003-03-21 Online:2003-11-24 Published:2003-11-24

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摘要： 在B3LYP/6-311G(d,p)和CCSD(T)/6-311G(d,p)水平上给出了HCO+NO2反应详细的势能面信息.计算结果表明,该反应采用两种无垒进攻方式,分别得到两种加合物H(O)CNO2和H(O)CONO.找到7种能量低于反应物且合理的产物及相应的反应路径.通过对热力学和动力学的分析,产物HONO+CO(P2,P3),HNO+CO2(P1)和H+CO2+NO(P6)的形成更为有利.计算结果同实验相符,且有助于深入了解HCO自由基的化学行为.

关键词: 甲酰基自由基, 势能面, 密度泛函, 过渡态

Abstract: The detail singlet potential energy surface of the HCONO2system iSInvestigated at the B3LYPand CCSD(T)(single-point) levels with 6-311G(d,p) basis set to study the possible reaction mechanism of HCOwith NO2From the reactant R(HCO+NO2), two associated adducts HC(O)NO2and H(O)CONO can be formed barrierlessly.Possible energetically allowed reaction pathways leading to seven low-lying dissociation products.The formation of HONO+CO(P2,P3), HNO+CO2(P1) and H+CO2+NO(P6) are more favorable than other products on the consideration of kinetic and thermodynamic factors.The calculated results presented in this paper agree with the previous experiment investigations and may be helpful for understanding this chemical behavior of formyl radical.

Key words: Formyl radical, Potential energy surface, Density function, Transition state

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