从头计算研究BP分子的势能曲线和光谱性质

王文宝; 于坤; 张晓美; 刘玉芳

doi:10.7498/aps.63.073302

摘要

利用高精度的量子化学从头计算MRCI+Q方法结合相关一致aug-cc-pVQZ基组计算了磷化硼分子X3，3-，5和5-态的势能曲线，计算所得的电子态在大键长位置处收敛于同一个离解极限B（2Pu）+P（4Su）. 为了得到更精确的结果，计算中首次纳入了旋轨耦合（SOC）效应，使得BP分子的4个-S态分裂成为15个态，其中30+ 态被确定为基态. 此外，SOC效应还使两个三重态X3和3-分裂出的0+和1态的势能曲线产生了避免交叉，表明在当前的计算中考虑SOC效应是非常必要的. 利用LEVEL8.0程序对计算所得的-S态和态的势能曲线进行拟合，得到了相应的光谱常数，通过与其他理论和实验工作进行比较，可知我们的结果更加精确、完整，可以为实验和理论方面进一步研究BP分子的光谱性质提供可靠的参考.

关键词:

Abstract

A high-precision quantum chemistry ab initio multi-reference configuration interaction method with aug-cc-pVQZ basis sets has been used to calculate the four states of BP molecule. The four -S states are X3, 3-, 5 and 5-, which are correlated to the lowest dissociation limit of B(2Pu)+P(4Su). Analysis of the electronic structures of -S states shows that the -S electronic states are essentially multi-configurational. We take the spin-orbit interaction into account for the first time so far as we know, which makes the four -S states split into fifteen states. 30+ state is confirmed to be the ground state. The SOC effect is essential for the BP molecule, which leads to the avoided crossings for 0+ and 1 states from X3 and 3-. Based on the PECs of -S and states, the accurate spectroscopic constants are obtained by solving the radial Schrdinger equation. The spectroscopic results may be conducive to further research on BP molecule in experiment and theory.

Keywords:

作者及机构信息

1.
河南师范大学物理与电子工程学院, 新乡 453007;

2.
兴义民族师范学院物理与工程技术学院, 兴义 562400

基金项目: 国家自然科学基金（批准号：11274096）和河南省高校科技创新团队（批准号：13IRTSTHN016）资助的课题.

Authors and contacts

1.
College of Physics & Electronic Engineering, Henan Normal University, Xinxiang 453007, China;

2.
College of Physics & Engineering, Xingyi Normal University for Nationalities, Xingyi 562400, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11274096), and the University Science and Technology Innovation Team Support Project of Henan Province, China (Grant no. 13IRTSTHN016).

参考文献

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施引文献

[1]	Zhang G F 1995 Infrared Technology 5 23 (in Chinese)[张贵锋1995 红外技术5 23]
[2]	Min X M, Cai K F, Nan C W 1998 Chinese Journal of Computation Phsics 15 445 (in Chinese) [闵新民, 蔡克峰, 南策文1998 计算物理15 445]
[3]	Gingerich K A 1972 The Journal of Chemical Physics 56 4239
[4]	Boldyrev A I, Simons J 1993 J. Phys. Chem. 97 6149
[5]	Gan Z T, Grant D J, Harrison R J, Dixon D A 2006 J. Chem. Phys. 125 124311
[6]	Linguerri R, Komiha N, Oswald R, Mitrushchenkov A, Rosmus P 2008 Chem. Phys. 346 1
[7]	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]
[8]	Li R, Lian K Y, Li Q N, Miao F J, Yan B, Jin M X 2012 Chin. Phys. B 21 123102
[9]	Li R, Wei C L, Sun Q X, Sun E P, Jin M X, Xu H F, Yan B 2013 Chin. Phys. B 22 123103
[10]	Le Roy R J 2007 LEVEL 8.0: A Computer Program for Solving the Radial Schrö dinger Equation for Bound and Quasibound Levels. University of Waterloo Chemical Physics Research Report CP-663
[11]	Werner H-J, Knowles P J 1985 J. Chem. Phys. 82 5053
[12]	Knowles P J, Werner H-J 1985 Chem. Phys. Lett. 115 259
[13]	Werner H-J, Knowles P J 1985 J. Chem. Phys. 89 5803
[14]	Knowles P J, Werner H-J 1988 Chem. Phys. Lett. 145 514
[15]	Berning A, Schweizer M, Werner H-J, Knowles P J, Palmieri P 2000 Mol. Phys. 98 1823
[16]	Yu K, Zhang X M, Liu Y F 2013 Acta Phys. Sin. 62 063301 (in Chinese) [于坤, 张晓美, 刘玉芳2013 62 063301]
[17]	Moore C E 1971 Atomic Energy Levels (Washington, DC: National Bureau of Standards)

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