BH+离子基态及激发态的势能曲线和跃迁性质的研究

罗华锋; 万明杰; 黄多辉

doi:10.7498/aps.67.20172409

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摘要

利用高精度的多组态相互作用及Davidson修正方法（MRCI+Q），采用ACV5Z-DK全电子基组计算了BH+离子的前4个离解通道B+（1Sg）+H（2Sg），B+（3Pu）+H（2Sg），B（2Pu）+H+（1Sg）和B+（1Pu）+H（2Sg）的9个S态的势能曲线.X2+，A2和B2+态的光谱常数和已有实验值符合得很好，其中b4+，32+，32和42+态的光谱常数为首次报道，32和42+态具有双势阱结构.预测了A2和B2+态的辐射寿命：（A2）=239.2 ns和（B2+）=431.2 ns.最后在考虑自旋轨道耦合效应下讨论了B2+与A2态的势能曲线的相交对激光冷却BH+离子的影响.

关键词:

作者及机构信息

1.
宜宾学院化学与工程学院, 宜宾 644007;

2.
宜宾学院, 计算物理四川省高等学校重点实验室, 宜宾 644007

通信作者: 黄多辉, hdhzhy912@163.com

基金项目: 国家自然科学基金理论物理专项（批准号：11647075）资助的课题.

参考文献

[1]	Nguyen J H V, Viteri C R, Hohenstein E G, Scherrill C D, Brown K R, Odom B 2011 New J. Phys. 13 063023
[2]	Li Y C, Meng T F, Li C L, Qiu X B, He X H, Yang W, Guo M J, Lai Y Z, Wei J L, Zhao Y T 2017 Acta Phys. Sin. 66 163101 (in Chinese)[李亚超, 孟腾飞, 李传亮, 邱选兵, 和小虎, 杨雯, 郭苗军, 赖云忠, 魏计林, 赵延霆 2017 物理学报 66 163101]
[3]	Kusunoki I 1984 Chem. Phys. Lett. 105 175
[4]	Almy G M, Horsfall Jr R B 1937 Phys. Rev. 51 491
[5]	Bauer S H, Herzberg G, Johns J W C 1964 J. Mol. Spectrosc. 13 256
[6]	Ottinger C, Reichmuth J 1981 J. Chem. Phys. 74 928
[7]	Ramsay D A, Sarre P J 1982 J. Chem. Soc.:Faraday Trans. 78 1331
[8]	Viteri C R, Gilkison A T, Rixon S J, Grant E R 2006 J. Chem. Phys. 124 144312
[9]	Rosmus P, Meyer W 1977 J. Chem. Phys. 66 13
[10]	Guest M F, Hirst D M 1981 Chem. Phys. Lett. 80 131
[11]	Klein R, Rosmus P, Werner H J 1982 J. Chem. Phys. 77 3559
[12]	Roothaan C C J 1960 Rev. Mod. Phys. 32 179
[13]	Knowles P J, Werner H J 1985 J. Chem. Phys. 82 5053
[14]	Knowles P J, Werner H J 1985 Chem. Phys. Lett. 115 259
[15]	Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[16]	Knowles P J Werner H J 1988 Chem. Phys. Lett. 145 514
[17]	Berning A, Schweizer M, Werner H J, Knowles P J, Palmieri P 2000 Mol. Phys. 98 1823
[18]	Woon D E, Dunning Jr T H 1995 J. Chem. Phys. 103 4572
[19]	Dunning Jr T H 1989 J. Chem. Phys. 90 1007
[20]	Murrell J N, Sorbie K S 1974 J. Chem. Soc.:Faraday Trans. 70 1552
[21]	Moore B C 1971 Atomic Energy Levels (Vol. 1) Natl. Stand Ref. Data Ser. Natl. Bur. Stand. No. 35 (Washington, DC:U.S. GPO) pp1-2 and 16-19
[22]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure, Constants of Diatomic Molecules (Vol. 4) (New York:van Nostrand Reinhold) p90
[23]	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 物理学报 58 6873]

施引文献

[1]	Nguyen J H V, Viteri C R, Hohenstein E G, Scherrill C D, Brown K R, Odom B 2011 New J. Phys. 13 063023
[2]	Li Y C, Meng T F, Li C L, Qiu X B, He X H, Yang W, Guo M J, Lai Y Z, Wei J L, Zhao Y T 2017 Acta Phys. Sin. 66 163101 (in Chinese)[李亚超, 孟腾飞, 李传亮, 邱选兵, 和小虎, 杨雯, 郭苗军, 赖云忠, 魏计林, 赵延霆 2017 物理学报 66 163101]
[3]	Kusunoki I 1984 Chem. Phys. Lett. 105 175
[4]	Almy G M, Horsfall Jr R B 1937 Phys. Rev. 51 491
[5]	Bauer S H, Herzberg G, Johns J W C 1964 J. Mol. Spectrosc. 13 256
[6]	Ottinger C, Reichmuth J 1981 J. Chem. Phys. 74 928
[7]	Ramsay D A, Sarre P J 1982 J. Chem. Soc.:Faraday Trans. 78 1331
[8]	Viteri C R, Gilkison A T, Rixon S J, Grant E R 2006 J. Chem. Phys. 124 144312
[9]	Rosmus P, Meyer W 1977 J. Chem. Phys. 66 13
[10]	Guest M F, Hirst D M 1981 Chem. Phys. Lett. 80 131
[11]	Klein R, Rosmus P, Werner H J 1982 J. Chem. Phys. 77 3559
[12]	Roothaan C C J 1960 Rev. Mod. Phys. 32 179
[13]	Knowles P J, Werner H J 1985 J. Chem. Phys. 82 5053
[14]	Knowles P J, Werner H J 1985 Chem. Phys. Lett. 115 259
[15]	Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[16]	Knowles P J Werner H J 1988 Chem. Phys. Lett. 145 514
[17]	Berning A, Schweizer M, Werner H J, Knowles P J, Palmieri P 2000 Mol. Phys. 98 1823
[18]	Woon D E, Dunning Jr T H 1995 J. Chem. Phys. 103 4572
[19]	Dunning Jr T H 1989 J. Chem. Phys. 90 1007
[20]	Murrell J N, Sorbie K S 1974 J. Chem. Soc.:Faraday Trans. 70 1552
[21]	Moore B C 1971 Atomic Energy Levels (Vol. 1) Natl. Stand Ref. Data Ser. Natl. Bur. Stand. No. 35 (Washington, DC:U.S. GPO) pp1-2 and 16-19
[22]	Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure, Constants of Diatomic Molecules (Vol. 4) (New York:van Nostrand Reinhold) p90
[23]	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 物理学报 58 6873]

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BH+离子基态及激发态的势能曲线和跃迁性质的研究

1. 宜宾学院化学与工程学院, 宜宾 644007;

2. 宜宾学院, 计算物理四川省高等学校重点实验室, 宜宾 644007

通信作者: 黄多辉, hdhzhy912@163.com

基金项目:

国家自然科学基金理论物理专项（批准号：11647075）资助的课题.

收稿日期: 2017-11-09

修回日期: 2017-12-08

刊出日期: 2019-02-20

摘要: 利用高精度的多组态相互作用及Davidson修正方法（MRCI+Q），采用ACV5Z-DK全电子基组计算了BH+离子的前4个离解通道B+（1Sg）+H（2Sg），B+（3Pu）+H（2Sg），B（2Pu）+H+（1Sg）和B+（1Pu）+H（2Sg）的9个S态的势能曲线.X2+，A2和B2+态的光谱常数和已有实验值符合得很好，其中b4+，32+，32和42+态的光谱常数为首次报道，32和42+态具有双势阱结构.预测了A2和B2+态的辐射寿命：（A2）=239.2 ns和（B2+）=431.2 ns.最后在考虑自旋轨道耦合效应下讨论了B2+与A2态的势能曲线的相交对激光冷却BH+离子的影响.

关键词:

Potential energy curves and transition properties for the ground and excited states of BH+ cation

1.
College of Chemistry & Chemical Engineering, Yibin University, Yibin 644007, China;

2.
Computational Physics Key Laboratory of Sichuan Province, Yibin University, Yibin 644007, China

Fund Project:

Project supported by the Special Foundation for Theoretical Physics Research of the National Natural Science Foundation of China (Grant No. 11647075).

Received Date: 09 November 2017

Accepted Date: 08 December 2017

Published Online: 20 February 2019

Abstract: BH+ cation is one of the candidates for laser cooling. The potential energy curves (PECs) for nine electronic states (X2+, A2, B2+, a4, b4+, 32+, 22, 32, 42+) relating to the B+(1Sg)+H(2Sg), B+(3Pu)+H(2Sg), B(2Pu)+H+(1Sg), and B+(1Pu)+H(2Sg) dissociation channels of BH+ cation are obtained using highly accurate multi-reference configuration interaction (MRCI) plus Davidson correction. All-electron basis sets AV5Z-DK for H and ACV5Z-DK for B are used in PEC calculations for the -i-S states of BH+ cation, respectively. In complete active space self-consistent field (CASSCF) calculation, H(1s2s2p3s3p) and B(2s2p) are chosen as active orbitals, B(1s) is the closed shell; in the MRCI calculation, the core-valence (CV) correction is considered, i.e., B(1s) shell is used for CV correlation. Spin-orbit coupling effects are considered with Breit-Pauli operators. Spectroscopic constants are fitted using the Murrell-Sorbie function. Spectroscopic constants for the X2+, A2, and B2+ states are in excellent agreement with the available experimental data; spectroscopic constants for the b4+, 32+, 32, and 42+ states are reported. Two potential wells for the 32 and 42+ states are found. The maximum fitting error of all electronic states is only 3.407 cm-1. In addition, PECs for the A2 and B2+ states are crossed at about 2.7 . Then, the transition dipole moments (TDMs) for the A2 X2+, B2+X2+, 32+X2+, B2+ A2, 32 X2+ and b4+ a4 transitions are also obtained. The strength for the B2+ A2 transition is very weak. Based on the accurate PECs and TDMs, the Franck-Condon factors and spontaneous radiative lifetimes are calculated. A strongly diagonal Franck-Condon factor (f00) for the A2X2+ transition is obtained, which equals 0.9414. Spontaneous radiative lifetime for the A2 and B2+ states is also predicted. i.e., (A2)=239.2 ns and (B2+)=431.2 ns. When SOC effect is considered, the A21/2 and B21/2+ states avoid crossing in the Franck-Condon region (R is about 2.7 ). Calculated f00 for the A21/2 X21/2+ transition is 0.9430; spontaneous radiative lifetime for the A21/2 is 239.0 ns. Our calculated results indicate that the influence for laser cooling BH+ cation via the crossing between B2+ and A2 states can be ignored.

Keywords:

multi-reference configuration interaction /
potential energy curves /
spectroscopic constants /
spontaneous radiative lifetimes

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