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OH, OCI, HOCI(1A')的从头算与势能曲线

韩晓琴 肖夏杰 刘玉芳

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OH, OCI, HOCI(1A')的从头算与势能曲线

韩晓琴, 肖夏杰, 刘玉芳

The ab initio and potential energy curve of OH, OCI and HOCI(1A')

Han Xiao-Qin, Xiao Xia-Jie, Liu Yu-Fang
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  • 采用Gassian09程序包中的多种方法对OH, OCI, HOCI分子的基态结构进行优化计算, 优选出QCISD/6-311G(2df), B3P86/6-311+G(2df)方法分别对OH(X2), OCI(X2)分子进行计算, 得到平衡核间距ROH=0.09696 nm, ROCI=0.1569 nm, 谐振频率(OH)=3745.37 cm-1, (OCI)=892.046 cm-1, 与实验结果非常符合. 用Murrell-Sorbie势能函数对OH和OCI分子的扫描势能点进行拟合, 其扫描点都与四参数Murrell-Sorbie函数拟合曲线符合得很好.优选出QCISD(T)/D95(df, pd)方法对HOCI分子进行计算, 得到基态为X1A', 键长ROH =0.0966 nm, 键角HOCI=102.3, 谐振频率1(a1)=738.69 cm-1, 2(b2)=1260.25 cm-1, 离解能De=2.24eV. 通过比较发现这些结果与实验值符合得很好,并优于文献报道的结果. 随后计算出了力常数, 在此基础上,推导出HOCI分子的多体展式势能函数.报道了HOCI分子对称伸缩振动势能图中在H+OCI HOCI反应通道上有一鞍点, H原子需要越过1.74eV的能垒才能生成HOCI的稳定结构, 在Cl+OHHOCI通道上不存在明显势垒, 容易形成稳定的HOCI分子.
    The possible ground state structures of OH, OCI and HOCI are optimized by using some methods included in Gaussian 09. Among them, the methods QCISD/6-311G(2df) and B3P86/6-311+G(2df) are the most suitable for the calculation of OH(X2) and OCI(X2) the spacings between eguilibrium nuclei ROH=0.09696 nm and ROCI=0.1569 nm, and harmonic freguencies (OH)=3745.37 cm-1 and (OCI)=892.046 cm-1 are calculated respectively. The calculation results are in good agreement with experimental results, Each potential energy curve obtained via scanning the single point energies of OH and OCI is well fit with the four-parameter Murrell-Sorbie function, according to which spectral data and force constants are deduced. The ground state of HOCI molecule is of 2A1' state, and the parameters of structure are ROH=0.0966 nm, HOCI 102.3, 1(a1)=738.69 cm-1, 2(b2)=1260.25 cm-1, De=2.24 eV with QCISD(T)/D95(df,pd). The present calculation results are in excellent agreement with the experimental values, and they are better than those given in the literature. And the force constants are calculated at the same time. The potential energy function of HOCI is derived from the many-body expansion theory. In the symmetric-stretch potential energy diagram, there is a saddle point in reaction channel H+OCI HOCI, and a stable HOCI molecule could be formed only when H atom crosses an energy barrier of 1.74 eV. However there is no clear energy barrier in the reaction channel Cl+OH HOCI, therefore a stable HOCI molecule can form easily.
    • 基金项目: 国家自然科学基金(批准号:60977063)和 河南省创新型科技人才队伍建设工程(批准号:124200510013) 资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 60977063) and the Innovation Scientists and Technicians Troop Construction Project of Henan Province, China (Grant No. 124200510013).
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    [11]

    Su F, Jack G C, Charlet R L 1979 J. Phys. Chem. 83 912

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    Thorn R P, Stief L J 1999 J. Phys. Chem. A 103 812

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    Wu D L, Pei L R, Xie A D, Wan H J 2009 J. Southwest Univ. National. 35 143 (in Chinese) [伍冬兰, 裴立荣, 谢安东, 万惠军2009西南民族大学学报 35 143]

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    Huber K P, Herzberg G 1979 Molecular Spectrum and Molecular Structure (IV) (New York: Van Nostrand)

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    Zhu J L, Ren T Q, Wang Q M 2009 Acta Phys. Sin. 58 3047 (in Chinese) [朱吉亮, 任廷琦, 王庆美2009 物理学报 58 3047]

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    Li Q, Zhu Z H 2006 Acta Phys. Sin. 55 1 (in Chinese) [李 权, 朱正和 2006 物理学报 55 1]

    [20]

    Fan X W, Geng Z D, Zhang Y S 2006 Acta Phys. Sin. 54 5614 (in Chinese) [樊晓伟, 耿振铎, 张岩松 2006 物理学报 54 5614]

    [21]

    Alfredo A, Miguel P 1992 J. Chem. Phys. 96 1265

    [22]

    Wedlock M R, Jost R, Rizzo T R 1997 J. Chem. Phys. 107 10344

    [23]

    Barnes R J, Dutton G, Sinha A 1997 J. Phys. Chem. A 101 8374

    [24]

    Cazzoli G, Degli E C, Vacera P G, Palmieri P 1984 Nuovo Cimento D 3 627

    [25]

    Francisco J S 1996 Chem. Phys. Lett. 260 485

    [26]

    Hassanzadeh P, Andrews L 1993 J. Phys. Chem. 97 4910

    [27]

    Han X Q, Jiang L J, Liu Y F 2010 Acta Phys. Sin. 59 1000 (in Chinese) [韩晓琴, 蒋丽娟, 刘玉芳 2010 物理学报 59 1000]

    [28]

    Shi D H, Liu H, Sun J F, Zhu Z L, Liu Y F 2010 Acta Phys. Sin. 59 227 (in Chinese) [施德恒, 刘慧, 孙金峰, 朱遵略, 刘玉芳 2010 物理学报 59 227]

    [29]

    Xiao X J, Han X Q, Liu Y F 2011 Acta Phys. Sin. 60 063102 (in Chinese) [肖夏杰, 韩晓琴, 刘玉芳 2011物理学报 60 063102]

    [30]

    Zhao J, Zeng H, Zhu Z H 2011 Acta Phys. Sin. 60 113102 (in Chinese) [赵俊, 曾晖, 朱正和 2011 物理学报 60 113102]

  • [1]

    Zhu Z H 1996 Atomic and Molecular Reaction Statics (Beijing: Science Press) (in Chinese) [朱正和 1996 原子分子反应静力学(北京:科学出版社)]

    [2]

    Zhu Z H, Yu H G 1997 Molecular Structure and Molecular Potential Energy Function (Beijing: Science Press) (in Chinese) [朱正和, 俞华根 1997 分子结构和势能函数 (北京:科学出版社)]

    [3]

    Grandinetti F, Vinciguerra V 2002 Int. J. Mass Spectrum. 216 285

    [4]

    Morrison M A, Weiguo S 1995 Computational Methods for Electron-Molecule Collisions (New York: Plenum)

    [5]

    Schwager I, Arkell A 1967 J. Am. Chem. Soc. 89 6006

    [6]

    Niki H, Maker P D, Savage C M, Brfitenbacn L P 1979 Chem. Phys. Lett. 66 325

    [7]

    Franz M G, Janice M H, Angel C D 1998 J. Phys. Chem. A 102 1514

    [8]

    Denis P A 2006 J. Phys. Chem. A 110 5887

    [9]

    Dominik H, Bernhard D 1999 Phys. Chem. Chem. Phys. 1 2667

    [10]

    Hedberg K, Badger R M 1951 J. Chem. Phys. 19 508

    [11]

    Su F, Jack G C, Charlet R L 1979 J. Phys. Chem. 83 912

    [12]

    Thorn R P, Stief L J 1999 J. Phys. Chem. A 103 812

    [13]

    Brown R A, Doren D J 1997 J. Phys. Chem. B 101 6308

    [14]

    Morse P M 1929 Phys. Rev. 34 57

    [15]

    Ellison F O 1963 J. Am. Chem. Soc. 85 3540

    [16]

    Wu D L, Pei L R, Xie A D, Wan H J 2009 J. Southwest Univ. National. 35 143 (in Chinese) [伍冬兰, 裴立荣, 谢安东, 万惠军2009西南民族大学学报 35 143]

    [17]

    Huber K P, Herzberg G 1979 Molecular Spectrum and Molecular Structure (IV) (New York: Van Nostrand)

    [18]

    Zhu J L, Ren T Q, Wang Q M 2009 Acta Phys. Sin. 58 3047 (in Chinese) [朱吉亮, 任廷琦, 王庆美2009 物理学报 58 3047]

    [19]

    Li Q, Zhu Z H 2006 Acta Phys. Sin. 55 1 (in Chinese) [李 权, 朱正和 2006 物理学报 55 1]

    [20]

    Fan X W, Geng Z D, Zhang Y S 2006 Acta Phys. Sin. 54 5614 (in Chinese) [樊晓伟, 耿振铎, 张岩松 2006 物理学报 54 5614]

    [21]

    Alfredo A, Miguel P 1992 J. Chem. Phys. 96 1265

    [22]

    Wedlock M R, Jost R, Rizzo T R 1997 J. Chem. Phys. 107 10344

    [23]

    Barnes R J, Dutton G, Sinha A 1997 J. Phys. Chem. A 101 8374

    [24]

    Cazzoli G, Degli E C, Vacera P G, Palmieri P 1984 Nuovo Cimento D 3 627

    [25]

    Francisco J S 1996 Chem. Phys. Lett. 260 485

    [26]

    Hassanzadeh P, Andrews L 1993 J. Phys. Chem. 97 4910

    [27]

    Han X Q, Jiang L J, Liu Y F 2010 Acta Phys. Sin. 59 1000 (in Chinese) [韩晓琴, 蒋丽娟, 刘玉芳 2010 物理学报 59 1000]

    [28]

    Shi D H, Liu H, Sun J F, Zhu Z L, Liu Y F 2010 Acta Phys. Sin. 59 227 (in Chinese) [施德恒, 刘慧, 孙金峰, 朱遵略, 刘玉芳 2010 物理学报 59 227]

    [29]

    Xiao X J, Han X Q, Liu Y F 2011 Acta Phys. Sin. 60 063102 (in Chinese) [肖夏杰, 韩晓琴, 刘玉芳 2011物理学报 60 063102]

    [30]

    Zhao J, Zeng H, Zhu Z H 2011 Acta Phys. Sin. 60 113102 (in Chinese) [赵俊, 曾晖, 朱正和 2011 物理学报 60 113102]

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  • 收稿日期:  2011-12-16
  • 修回日期:  2012-01-08
  • 刊出日期:  2012-08-05

OH, OCI, HOCI(1A')的从头算与势能曲线

  • 1. 河南师范大学物理与信息工程学院, 新乡 453007;
  • 2. 商丘师范学院物理与电气信息学院, 商丘 476000;
  • 3. 河南质量工程职业学院, 平顶山 467000
    基金项目: 国家自然科学基金(批准号:60977063)和 河南省创新型科技人才队伍建设工程(批准号:124200510013) 资助的课题.

摘要: 采用Gassian09程序包中的多种方法对OH, OCI, HOCI分子的基态结构进行优化计算, 优选出QCISD/6-311G(2df), B3P86/6-311+G(2df)方法分别对OH(X2), OCI(X2)分子进行计算, 得到平衡核间距ROH=0.09696 nm, ROCI=0.1569 nm, 谐振频率(OH)=3745.37 cm-1, (OCI)=892.046 cm-1, 与实验结果非常符合. 用Murrell-Sorbie势能函数对OH和OCI分子的扫描势能点进行拟合, 其扫描点都与四参数Murrell-Sorbie函数拟合曲线符合得很好.优选出QCISD(T)/D95(df, pd)方法对HOCI分子进行计算, 得到基态为X1A', 键长ROH =0.0966 nm, 键角HOCI=102.3, 谐振频率1(a1)=738.69 cm-1, 2(b2)=1260.25 cm-1, 离解能De=2.24eV. 通过比较发现这些结果与实验值符合得很好,并优于文献报道的结果. 随后计算出了力常数, 在此基础上,推导出HOCI分子的多体展式势能函数.报道了HOCI分子对称伸缩振动势能图中在H+OCI HOCI反应通道上有一鞍点, H原子需要越过1.74eV的能垒才能生成HOCI的稳定结构, 在Cl+OHHOCI通道上不存在明显势垒, 容易形成稳定的HOCI分子.

English Abstract

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