SN-分子离子的势能函数和光谱常数研究

李松; 韩立波; 陈善俊; 段传喜

doi:10.7498/aps.62.113102

摘要

采用耦合簇CCSD(T)方法结合系列相关一致基组aug-cc-pVXZ (X=D,T,Q,5) 对基态SN-分子离子(X3∑-) 进行了结构优化和单点能扫描计算. 用四种方法进行基组外推得到该体系的平衡核间距Re=0.15852 nm, 谐振频率ωe=948.05 cm-1, 离解能De=3.934 eV均与实验数据符合得很好. 对单点能扫描结果用9参数Murrell-Sorbie势能函数进行了最小二乘拟合, 得到了体系的解析势能函数表达式, 并进一步推导出了体系的力常数和光谱常数. 拟合所得势能曲线准确地再现了SN-分子离子的离解能和平衡结构特征. 通过求解核运动的径向薛定谔方程, 得到了无转动SN- (X3∑-) 的全部振动态, 并进一步计算出了各振动能级相应的分子常数. 与实验结果及其他理论研究结果的对比表明, 本文关于SN-分子离子平衡常数和光谱常数的计算结果达到了较高的精度, 能为进一步的实验探测和理论研究提供参考依据.

关键词:

Abstract

The molecular structure of the ground electronic state (X3∑-) of SN- molecular ion has been calculated by using the CCSD(T) method in combination with the correlation-consistent basis sets aug-cc-pVXZ (X=D,T,Q,5). The equilibrium internuclear distance Re , harmonic frequency ωe and dissociation energy De of the molecular ion are derived and are extrapolated to the complete basis set limit. Comparisons of corresponding parameters between this work and those reported previously indicate our results agree well with the experimental data. A reliable potential energy curve is obtained and is perfectly reproduced in the form of the Murrell-Sorbie analytical potential function. we utilized have the potential energy curve to calculate the relevant spectroscopic parameters of the ground state of the system. The vibrational levels and corresponding molecular constants for the X3∑- state are obtained by solving the radial Schrödinger equation of the nuclear motion. Calculations in the present work indicate that an improvement in theoretical computations of SN- molecular ion is achieved.

Keywords:

作者及机构信息

1.
长江大学物理科学与技术学院, 荆州 434023;

2.
华中师范大学物理科学与技术学院, 武汉 430079

基金项目: 湖北省教育厅重点项目 (批准号: D20101303) 、湖北省高等学校优秀中青年科技创新团队计划项目 (批准号: T201204) 和长江大学博士启动金项目资助的课题.

Authors and contacts

1.
College of Physical Science and Technology, Yangtze University, Jingzhou 434023, China;

2.
College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China

Funds: Project supported by the Research Foundation of Education Bureau of Hubei Province, China (Grant No. D20101303), the Technology Creative Project of Excellent Middle & Young Team of Hubei Province, China (Grant No. T201204), and the Scientific Research Starting Foundation for Ph. D. of Yangtze University, China.

参考文献

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[7]	Kelly P F, Woollins J D 1986 Polyhedron 5 607
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[10]	Bruna P J, Grain F 1987 J. Phys. B: At. Mol. Phys. 20 5967
[11]	Peterson K A, Woods R C 1990 J. Chem. Phys. 93 1876
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[17]	Helgaker T, Klopper W, Koch H, Noga J 1997 J. Chem. Phys. 106 9639
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[22]	Balabanov N B, Peterson K A 2003 J. Phys. Chem. A 107 7465
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[26]	Huang D H, Wang P H, Zhu Z H 2008 Acta Chim. Sinica 66 1915 (in Chinese) [黄多辉, 王藩侯, 朱正和 2008 化学学报 66 1915]
[27]	Zhao J, Zeng H, Zhu Z H 2011 Acta Phys. Sin. 60 113102 (in Chinese) [赵俊, 曾晖, 朱正和 2011 60 113102]
[28]	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 分子结构与势能函数 (北京: 科学出版社)]
[29]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Van Nostrand Reinhold Company, New York)
[30]	Wang R, Jiang G, Meng D Q, Zhu Z H 2009 Acta Phys. Chim. Sin. 25 1103 (in Chinese) [王蓉, 蒋刚, 蒙大桥, 朱正和 2009 物理化学学报 25 1103]
[31]	Wang X Q, Yang C L, Su T, Wang M S 2009 Acta Phys. Sin. 58 6873 (in Chinese) [王新强, 杨传路, 苏涛, 王美山 2009 58 6873]
[32]	Wang J M, Sun J F 2011 Acta Phys. Sin. 60 123103 (in Chinese) [王杰敏, 孙金锋 2011 60 123103]

施引文献

[1]	Chivers T 2005 A Guide to Chalcogen-Nitrogen Chemistry (Singapore: World Scientific Publishing Co.)
[2]	Oakley R T 1988 Prog. Inorg. Chem. 36 299
[3]	Roesky H W 1979 Adv. Inorg. Chem. Radiochem. 22 239
[4]	Bojes J, Chivers T, Oakley R T, Womershäuser G, Schnauber M 2007 Binary Cyclic Nitrogen-Sulfur Anions, in Inorganic Syntheses, Volume 25 (Hoboken: John Wiley & Sons, Inc.)
[5]	Greene R L, Street G B, Suter L J 1975 Phys. Rev. Lett. 34 577
[6]	Labes M M, Love P, Nichols L F 1979 Chem. Rev. 79 1
[7]	Kelly P F, Woollins J D 1986 Polyhedron 5 607
[8]	Chivers T, Edelmann F 1986 Polyhedron 5 1661
[9]	Burnett S M, Felgerle C S, Stevens A E, Lineberger W C 1982 J. Phys. Chem. 86 4486
[10]	Bruna P J, Grain F 1987 J. Phys. B: At. Mol. Phys. 20 5967
[11]	Peterson K A, Woods R C 1990 J. Chem. Phys. 93 1876
[12]	Czernek J, Živný O 2004 Chem. Phys. 303 137
[13]	Zhu Z H 1996 Atomic and molecular Reaction Statics (Beijing: Science Press) (in Chinese) [朱正和 1996 原子与分子反应静力学 (北京: 科学出版社)]
[14]	Jenson F 2005 Theor. Chem. Acc. 113 267
[15]	Peterson K A, Woon D E, Dunning T H Jr. 1994 J. Chem. Phys. 100 7410
[16]	Feller D 1992 J. Chem. Phys. 96 6104
[17]	Helgaker T, Klopper W, Koch H, Noga J 1997 J. Chem. Phys. 106 9639
[18]	Martin J M L 1996 Chem. Phys. Lett. 259 669
[19]	Dixon D A, de Jong W A, Peterson K A, McMahon T B 2005 J. Phys. Chem. A 109 4073
[20]	Feller D, Peterson K A, Crawford T D 2006 J. Chem. Phys. 124 054107
[21]	Feller D, Peterson K A 2007 J. Chem. Phys. 126 114105
[22]	Balabanov N B, Peterson K A 2003 J. Phys. Chem. A 107 7465
[23]	Balabanov N B, Peterson K A 2005 Theor. Chem. Acc. 114 283
[24]	Murrell J N, Sorbie K S 1974 J. Chem. Soc. Faraday Trans. 2 1552
[25]	Kong F J, Du J G, Jiang G 2008 Acta Phys. Sin. 57 149 (in Chinese) [孔凡杰, 杜际广, 蒋刚 2008 57 149]
[26]	Huang D H, Wang P H, Zhu Z H 2008 Acta Chim. Sinica 66 1915 (in Chinese) [黄多辉, 王藩侯, 朱正和 2008 化学学报 66 1915]
[27]	Zhao J, Zeng H, Zhu Z H 2011 Acta Phys. Sin. 60 113102 (in Chinese) [赵俊, 曾晖, 朱正和 2011 60 113102]
[28]	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 分子结构与势能函数 (北京: 科学出版社)]
[29]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Van Nostrand Reinhold Company, New York)
[30]	Wang R, Jiang G, Meng D Q, Zhu Z H 2009 Acta Phys. Chim. Sin. 25 1103 (in Chinese) [王蓉, 蒋刚, 蒙大桥, 朱正和 2009 物理化学学报 25 1103]
[31]	Wang X Q, Yang C L, Su T, Wang M S 2009 Acta Phys. Sin. 58 6873 (in Chinese) [王新强, 杨传路, 苏涛, 王美山 2009 58 6873]
[32]	Wang J M, Sun J F 2011 Acta Phys. Sin. 60 123103 (in Chinese) [王杰敏, 孙金锋 2011 60 123103]

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