CO分子振转光谱的理论研究

doi:10.3964/j.issn.1000-0593(2018)04-1001-06

摘要
参考文献
相关文章 (15)

全文: PDF (1609 KB)
输出: BibTeX | EndNote (RIS)

摘要：采用从头算的多参考组态相互作用(MRCI)方法并结合基组aug-cc-pCVQZ计算了CO分子基态(X¹Σ⁺)的势能曲线和偶极矩曲线，得到的势能曲线、偶极矩曲线分别与RKR势、文献的偶极矩曲线吻合较好。利用所得的势能，求解双原子分子核运动的Schrdinger方程找到了CO分子X¹Σ⁺态转动量子数J=0时的70个振动态，对于每一振动态，分别计算了其振动能级G(v)、转动惯性常数B_v和离心畸变常数D_v，并把计算结果与已知的42个实验值做了详细比较，结果表明，计算的振动能级G(v)、转动惯性常数B_v、离心畸变常数D_v与实验值符合较好。利用G(v)，B_v导出的光谱常数[谐振频率ω_e(2 160.1 cm^-1)、非谐振频率ω_eχ_e(13.1 cm^-1)、转动常数B_e(1.918 cm^-1)、振转耦合常数α_e(0.017 3 cm^-1)]也与实验值的光谱常数[ω_e(2 169.8 cm^-1)，ω_eχ_e(13.3 cm^-1)，B_e(1.931 cm^-1)，α_e(0.017 5 cm^-1)]较为符合，这在一定程度上证明了方法MRCI/Aug-cc-pCVQZ对CO分子基态性质的计算是合适而可靠的。利用乘积近似方法计算了CO分子在常温、中温、高温时的配分函数，在此基础上，计算了CO分子在T=296 K时的1-0跃迁带的谱线强度，通过比较发现，计算所得的线强度与HITRAN数据库符合较好。进一步计算的CO分子X¹Σ⁺态1-0，2-0，3-0，4-0，2-1，3-1和4-1跃迁带的带强度也与实验值较为吻合，同时首次计算了CO分子X¹Σ⁺态3-2跃迁带、4-2跃迁带的线强度及带强度。

关键词：CO分子; 配分函数; 振动能级; 光谱常数; 线强度; 带强度

Abstract：The potential energy curve (PEC) and dipole moment curve (DMC) for the ground state (X¹Σ⁺) of CO molecule have been computed using the multi-reference configuration interaction (MRCI) method with aug-cc-pCVQZ basis sets. Results showed that the calculated PEC, DMC are in accord with RKR, reference, respectively. With the potential energy obtained at the MRCI/aug-cc-pCVQZ level of theory, 70 vibrational states (J=0) of the ground state of CO molecule are obtained by numerically solving the radical Schrdinger equation of nuclear motion. For each vibrational state, the vibrational energy levels G(v), the inertial rotation constants B_v and the centrifugal distortion constants D_v are reported, which accord well with the experimental values. The inertial rotation constants B_v, vibrational energy levels G(v) were fitted to determine spectroscopy constants, which the rotation coupling constant ω_e(2 160.1 cm^-1), the anharmonic constant ω_eχ_e(13.3 cm^-1), the equilibrium rotation constant B_e(1.931 cm^-1) and the vibration-rotation coupling constant α_e(0.017 5 cm^-1) are in good agreement with the experiment data [ω_e(2 169.8 cm^-1), ω_eχ_e(13.3 cm^-1), B_e(1.931 cm^-1), α_e(0.017 5 cm^-1)], it is evident that MRCI/Aug-cc-pCVQZ is reliable for the calculation for the ground state of CO molecule. The line intensity of 1-0 transition band for the ground state of CO molecule is calculated by directly calculating the partition function at 296 K, the agreement between the calculated line intensity data and the data in HITRAN database is fairly good at 296 K. Band intensities of 1-0，2-0，3-0，4-0，2-1，3-1，4-1 bands are calculated for the ground state of CO molecule, which are in better agreement with the experimental values. Therefore, the line intensities and band intensities of 3-2 transition band, 4-2 transition band are firstly calculated.

Key words：CO molecule; partition function; Vibrational energy levels; Spectroscopic constants; Line intensity; Band intensity

收稿日期: 2016-12-27 修订日期: 2017-04-30

中图分类号:

O561.3

基金资助: 国家自然科学基金项目(11264008, 11364007)，贵州省普通高等学校低维凝聚态物理重点实验室(黔教合KY字[2016]002)，贵州省教育厅自然科学基金项目(黔教科2010016)，贵州省科学技术基金(黔科合J字[2013]2242), 贵州师范大学2014年度研究生创新基金项目(研创2014(19))资助

通讯作者: 宋晓书 E-mail: songxs1227@163.com

作者简介: 张学富，1989年生，贵州师范大学物理与电子科学学院研究生 e-mail: 1208031868@qq.com

引用本文:

张学富，吕兵，宋晓书，令狐荣锋. CO分子振转光谱的理论研究[J]. 光谱学与光谱分析, 2018, 38(04): 1001-1006.
ZHANG Xue-fu, Lü Bing, SONG Xiao-shu, LINGHU Rong-feng. Theoretical Study of Ro-Vibrational Spectrum of CO Molecule. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(04): 1001-1006.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2018)04-1001-06 或 https://www.gpxygpfx.com/CN/Y2018/V38/I04/1001

[1] LIU Yan-de, JIN Tan-tan(刘燕德, 靳昙昙). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2015, 35(9): 2567.
[2] Storey J W V, Waston D M, Townes C H, et al. The Astrophysical Journal, 1981, 247: 136.
[3] Toth R A, Hunt R H, Plyler E K. Journal of Molecular Spectroscopy, 1969, 32(1): 85.
[4] ZHANG Jun-li(张俊丽). Study(1, 0), (4, 2) and (6, 1) in the Triplet Band of CO(CO分子三重带系(1, 0), (4, 2)和(6, 1)带分析). Shanghai: East China Normal University(上海: 华东师范大学), 2010.
[5] Bachrach S M, Chiles R A, Dykstra C E. The Journal of Chemical Physics, 1981, 75(5): 2270.
[6] Kobus J, Moncrieff D, Wilson D. Journal of Physics B: Atomic, Molecular and Optical Physics, 1994, 27(21): 5139.
[7] Cooper D L, Kirby K. The Journal of Chemical Physics, 1987, 87(1): 424.
[8] Rothman L S, Gordon I E, Babikov Y, et al. Journal of Quantitative Spectroscopy & Radiative Transfer, 2013, 130: 4.
[9] Rydberg R. Zeitschrift für Physik, 1932, 73(5): 376.
[10] Klein O. Zeitschrift für Physik, 1932, 76(3): 226.
[11] Rydberg R. Zeitschrift für Physik, 1933, 80(7): 514.
[12] Rees A L G. Proceedings of the Physical Society, 1947, 59(6): 998.
[13] YANG Chuan-lu, HUANG Yu-jun, ZHANG Fu-zeng, et al(杨传路, 黄钰珺, 张福增, 等). Journal of Atomic and Molecular Physics(原子与分子物理学报), 2004, 21(2): 315.
[14] HUANG Li-juan(黄丽娟). The Quantum Chemical Calculation of O₂ and CO(M. S. Dissertation)(O₂分子和CO分子的量化计算研究(硕士学位论文)). Shanghai: East China Normal University(上海：华东师范大学), 2013.
[15] Chandra S, Sharma A K, Khan Z H. Pramana, 1996, 47(1): 65.
[16] Coxon J A, Hajigeorgiou P G. Canadian Journal of Physics, 1992, 70(1): 40.
[17] Falzon C T, Chong D P, Wang F. Journal of Computational Chemistry, 2005, 27(2): 163.
[18] Lu P F, Yan L, Yu Z Y, et al. Communications in Theoretical Physics, 2013, 59(2): 193.
[19] Xu G L, Lv W J, Liu Y F, et al. Journal of Molecular Structure: THEOCHEM, 2008, 866(1): 79.
[20] Huberg K P, Herzberg G. Molecular Spectra and Molecular Structure: IV. Constants of diatomicmolecules. Van Nostrand Reinhold Company: New York, 1979.
[21] Gamache R R, Hawkins R L, Rothman L S. Journal of Molecular Spectroscopy, 1990, 142(2): 205.
[22] Gamache R R, Hawkins R L, Rothman L S. Journal of Molecular Structure, 2000, 517: 407.
[23] McDowell R S. The Journal of Chemical Physics, 1988, 88(1): 356.
[24] Hezberg G. Molecular Spectra and Molecular Structure (Ⅱ): Infrared and Raman Spectra of Polyatomic Molecules. Van Nostrand Reinhold Company: New York, 1947.
[25] Le Roy R J. Level 8.0: A Computer Program for Solving the Radial Schrdinger Equation for Bound and Quasibound Levels, University of Waterloo Chemical Physics Research Report 2007. NO.CP-663.