HSOCl的平衡构型及其相对稳定性的理论研究.PDF

化学通报 2005 年 第 68 卷 w094 HSOCl 的平衡构型及其相对稳定性的理论研究 1 2 2 杨迎春 陈文凯 徐永福 胡非 叶芝祥 (成都信息工程学院地球环境科学系 成都 610041 1 福州大学化学系 福州 350002 2 中国科学院大气物理研究所大气边界层物理和大气化学国家重点实验室 北京 100029) 摘 要 采用量子化学中的 HF 方法，在 aug-cc-pvtz 基组水平上，全优化得到了 HSOCl 体系势 能面上四个异构体和三个过渡态，并分析了这些异构体的结构及异构化过程。在得到的异构体中，有 两个异构体是动力学较稳定的，分别是线型的 HOSCl 和分叉型的 OS(H)Cl，这两个异构体在实验中应 该可以观察到。同时采用内禀反应坐标(IRC)证实了所得到过渡态的真实性。 关键词 HSOCl 体系 势能面 异构化 动力学稳定性 A Theoretical Study on the Equilibrium Structures and Relative Stability of HSOCl Yang Yingchun, Chen Wenkai 1 , Xu Yongfu 2 , Hu Fei 2 , Ye Zhixiang (Department of Earth and Environmental Sciences, Chengdu University of Information Technology, Chengdu 610041 1 Department of Chemistry, Fuzhou University, Fuzhou 350002 2 State Key Laboratory of Atmospheric Boundary Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029) Abstract Ab initio Hartree-Fock theory with aug-cc-pvtz basis set level is used to investigate the equilibrium structures and isomerization of HSOCl system. All the transition states have been calculated and conformed by the intrinsic reaction coordinate (IRC). The structures and isomerizations of the optimized isomers are discussed. In all the optimized four isomers, two species, linear HOSCl and branched OS(H)Cl are predicted as the kinetically stable isomers in this paper, and they may be detected experimentally. Key words HSOCl system, Potential energy surface(PES), Isomerization, Kinetic stability