BCl分子X1Σ+, a3Π和A1Π态的光谱性质

刘慧; 邢伟; 施德恒; 孙金锋; 朱遵略

doi:10.7498/aps.63.123102

摘要

采用Davidson修正的内收缩多参考组态相互作用方法（MRCI+Q）及Dunning等的相关一致基aug-cc-pV6Z计算了BCl分子X1Σ+，a3Π和A1Π态的势能曲线. 利用总能量外推公式，将这3个态的总能量分别外推至完全基组极限. 对势能曲线进行核价相关修正及相对论修正计算，得到了同时考虑这两种修正的外推势能曲线. 拟合势能曲线得到了3个态的主要光谱常数Te，Re，ωe，ωexe，Be，αe 和De 等，它们与已有的实验结果较为一致. 利用获得的势能曲线，通过求解双原子分子核运动的径向Schrödinger方程，找到了BCl分子X1Σ+，a3Π 和A1Π态的全部振动态，并得到了相应的振动能级和惯性转动常数等分子常数. 还计算了a3Π–X1Σ+ 和A1Π–X1Σ+的跃迁偶极矩、Franck-Condon 因子，预测了若干跃迁的辐射寿命.

关键词:

Abstract

The X1Σ+, a3Π and A1Π states of BCl molecule are studied using the highly accurate valence internally contracted multireference configuration interaction approach including the Davidson modification. The Dunning's correlation-consistent basis sets, aug-cc-pV6Z and aug-cc-pV5Z, are used in the study. To obtain more reliable results, the potential energy curves (PECs) of three electronic states are extrapolated to the complete basis set limit by the two-point total-energy extrapolation scheme. The effects of the core-valence correlation and relativistic corrections on the PECs are taken into account. By fitting these PECs, the spectroscopic parameters (Te, Re, ωe, ωexe, Be, αe and De) of the X1Σ+, a3Π and A1Π states of BCl are determined. These parameter values coincide with the experimental results. In addition, the whole vibrational states for X1Σ+, a3Π and A1Π states at J =0 (J is the rotational quantum number) are determined by numerically solving the radical Schrödinger equation of the nuclear motion of diatomic molecules. For each vibrational state, the vibrational level and inertial rotation constants are obtained, which are in excellent accordance with the experimental results. With the potential energy curves obtained at MRCI+Q/56+CV+DK level and the MRCI wave functions, the Franck-Condon factors, radiative lifetime of transition from a3Π and A1Π to the ground state are computed.

Keywords:

作者及机构信息

1.
信阳师范学院物理电子工程学院, 信阳 464000;

2.
河南师范大学物理与信息工程学院, 新乡 453007

基金项目: 国家自然科学基金（批准号：61077073）、河南省科技计划（批准号：142300410201）和河南省教育厅科技计划重点项目（批准号：14B140023）资助的课题.

Authors and contacts

1.
College of Physics and Electronic Engineering, Xinyang Normal University, Xinyang 464000, China;

2.
College of Physics and Information Engineering, Henan Normal University, Xinxiang 453007, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 61077073), the Science and Techno- logy Project of Henan Province, China (Grant No. 142300410201), and the Program for Science and Technology of the Educational Bureau of Henan Province, China (Grant No. 14B140023).

参考文献

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[2]	Miescher E 1935 Helv. Phys. Acta 8 279
[3]	Herzberg G, Hushley W 1941 Can. J. Res. 19 127
[4]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (New York: Van Nostrand Reinhold) p74
[5]	Maki A G, Lovas F J, Suenram R D 1982 J. Mol. Spectrosc. 91 424
[6]	Endo Y, Saito S, Hirota E 1983 Bull. Chem. Soc. Jpn. 56 3410
[7]	Bredohl H, Dubois I, Houbrechts Y, Nzohabonayo P 1984 J. Phys. B: At. Mol. Phys. 17 209
[8]	Bredohl H, Dubois I, Mélen F 1987 J. Mol. Spectrosc. 121 135
[9]	Verma R D 1995 J. Mol. Spectrosc. 169 295
[10]	Bozhenko K V, Charkin O P 1977 Zh. Strukturnoi Khimii 18 219
[11]	Peterson K A, Woods R C 1987 J. Chem. Phys. 87 4409
[12]	Mller-Plathe F, Diercksen G H F 1987 Int. J. Quantum Chem. 32 595
[13]	Pyykkö P 1987 Chem. Phys. Lett. 134 575
[14]	Schlegel H B, Harris S J 1994 J. Phys. Chem. 98 11178
[15]	Bauschlicher C W, Ricca A 1999 J. Phys. Chem. A 103 4313
[16]	Irikura K K, Johnson R D, Hudgens J W 2000 J. Phys. Chem. A 104 3800
[17]	Baeck K K, Joo Y 2001 Chem. Phys. Lett. 337 190
[18]	Peterson K A, Dunning T H 2002 J. Chem. Phys. 117 10548
[19]	Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 8 61
[20]	Richartz A, Buenker R J, Peyerimhoff S D 1978 Chem. Phys. 28 305
[21]	Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[22]	Knowles P J 1988 Chem. Phys. Lett. 145 514
[23]	Dunning T H 1989 J. Chem. Phys. 90 1007
[24]	Van Mourik T, Dunning T H 2000 Int. J. Quantum Chem. 76 205
[25]	De Jong W A, Harrison R J, Dixon D A 2001 J. Chem. Phys. 114 48
[26]	Xing W, Liu H, Shi D H, Sun J F, Zhu Z L 2013 Acta Phys. Sin. 62 043101 (in Chinese) [邢伟, 刘慧, 施德恒, 孙金峰, 朱遵略 2013 62 043101]
[27]	Wang J M, Feng H Q, Sun J F, Shi D H, Li W T, Zhu Z L 2013 Acta Phys. Sin. 62 013105 (in Chinese) [王杰敏, 冯恒强, 孙金锋, 施德恒, 李文涛, 朱遵略 2013 62 013105]
[28]	Li R, Lian K Y, Li Q N, Miao F J, Yan B, Jin M X 2012 Chin. Phys. B 21 123102
[29]	Yan B, Liu L L, Wei C L, Guo J, Zhang Y J 2011 Chin. Phys. B 20 043101
[30]	Liu H, Xing W, Shi D H, Sun J F, Zhu Z L 2013 Acta Phys. Sin. 62 203104 (in Chinese) [刘慧, 邢伟, 施德恒, 孙金峰, 朱遵略 2013 62 203104]
[31]	Halkier A, Helgaker T, Jørgensen P, Klopper W, Koch H, Olsen J, Wilson A K 1998 Chem. Phys. Lett. 286 243
[32]	Reiher M, Wolf A 2004 J. Chem. Phys. 121 2037
[33]	Wolf A, Reiher M, Hess B A 2002 J. Chem. Phys. 117 9215

施引文献

[1]	Jevons W 1924 Proc. R. Soc. A 106 174
[2]	Miescher E 1935 Helv. Phys. Acta 8 279
[3]	Herzberg G, Hushley W 1941 Can. J. Res. 19 127
[4]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (New York: Van Nostrand Reinhold) p74
[5]	Maki A G, Lovas F J, Suenram R D 1982 J. Mol. Spectrosc. 91 424
[6]	Endo Y, Saito S, Hirota E 1983 Bull. Chem. Soc. Jpn. 56 3410
[7]	Bredohl H, Dubois I, Houbrechts Y, Nzohabonayo P 1984 J. Phys. B: At. Mol. Phys. 17 209
[8]	Bredohl H, Dubois I, Mélen F 1987 J. Mol. Spectrosc. 121 135
[9]	Verma R D 1995 J. Mol. Spectrosc. 169 295
[10]	Bozhenko K V, Charkin O P 1977 Zh. Strukturnoi Khimii 18 219
[11]	Peterson K A, Woods R C 1987 J. Chem. Phys. 87 4409
[12]	Mller-Plathe F, Diercksen G H F 1987 Int. J. Quantum Chem. 32 595
[13]	Pyykkö P 1987 Chem. Phys. Lett. 134 575
[14]	Schlegel H B, Harris S J 1994 J. Phys. Chem. 98 11178
[15]	Bauschlicher C W, Ricca A 1999 J. Phys. Chem. A 103 4313
[16]	Irikura K K, Johnson R D, Hudgens J W 2000 J. Phys. Chem. A 104 3800
[17]	Baeck K K, Joo Y 2001 Chem. Phys. Lett. 337 190
[18]	Peterson K A, Dunning T H 2002 J. Chem. Phys. 117 10548
[19]	Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 8 61
[20]	Richartz A, Buenker R J, Peyerimhoff S D 1978 Chem. Phys. 28 305
[21]	Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[22]	Knowles P J 1988 Chem. Phys. Lett. 145 514
[23]	Dunning T H 1989 J. Chem. Phys. 90 1007
[24]	Van Mourik T, Dunning T H 2000 Int. J. Quantum Chem. 76 205
[25]	De Jong W A, Harrison R J, Dixon D A 2001 J. Chem. Phys. 114 48
[26]	Xing W, Liu H, Shi D H, Sun J F, Zhu Z L 2013 Acta Phys. Sin. 62 043101 (in Chinese) [邢伟, 刘慧, 施德恒, 孙金峰, 朱遵略 2013 62 043101]
[27]	Wang J M, Feng H Q, Sun J F, Shi D H, Li W T, Zhu Z L 2013 Acta Phys. Sin. 62 013105 (in Chinese) [王杰敏, 冯恒强, 孙金锋, 施德恒, 李文涛, 朱遵略 2013 62 013105]
[28]	Li R, Lian K Y, Li Q N, Miao F J, Yan B, Jin M X 2012 Chin. Phys. B 21 123102
[29]	Yan B, Liu L L, Wei C L, Guo J, Zhang Y J 2011 Chin. Phys. B 20 043101
[30]	Liu H, Xing W, Shi D H, Sun J F, Zhu Z L 2013 Acta Phys. Sin. 62 203104 (in Chinese) [刘慧, 邢伟, 施德恒, 孙金峰, 朱遵略 2013 62 203104]
[31]	Halkier A, Helgaker T, Jørgensen P, Klopper W, Koch H, Olsen J, Wilson A K 1998 Chem. Phys. Lett. 286 243
[32]	Reiher M, Wolf A 2004 J. Chem. Phys. 121 2037
[33]	Wolf A, Reiher M, Hess B A 2002 J. Chem. Phys. 117 9215

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