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低激发态CN自由基光谱参数的理论研究

Theoretical Study on Spectroscopic Properties of the Low Excited States for CN Radical

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摘要

CN自由基在碳化物的燃烧过程中一直扮演着重要的角色。采用量化计算方法对CN自由基进行了从头计算。首先利用Hartree-Fock自洽场方法进行轨道计算,再使用完全活性空间自洽场对轨道进行优化,然后采用多参考组态相互作用的方法计算了在006到07 nm的核间距范围内CN自由基3个低激发态(X2Σ+,A2Π和B2Σ+)的势能曲线。为了进一步提高计算的精度,考虑相对论效应选择aug-cc-pV5Z-dk相关一致基组。求解径向薛定谔方程,得到了各电子态振-转能级的能量和振-转常数,并拟合获得这些电子态的光谱常数(Te,Re,ωe,ωeχe,Be,αe)及Franck-Condon因子,其与实验结果基本一致。同时,计算CN自由基A2∏-X2∑+的跃迁偶极矩,并得到5个低振动能级的辐射寿命τ和振子强度f00。计算获得辐射寿命为~4 μs,与实验测量结果符合较好,为研究燃烧过程中动力学行为提供了理论依据。

Abstract

CN radical plays an important role in the combustion of carbides.The low-excited state of CN was investigated by the ab initio calculation.Firstly,the molecular orbitals were determined by the Hartree-Fock self-consistent field approximation and optimized to use the complete active space self-consistent field theory.Then,the potential energy curves of three low excited states (X2Σ+,A2Π,and B2Σ+) for CN in the range of nuclear distance from 006 to 07 nm were obtained through multi-reference configuration interaction method.Considering the relativistic effects,the aug-cc-pV5Z-dk correlation-consistent basis set was selected in order to further improve the accuracy of the calculation.The vibration-rotation energy and constants of these electronic states were derived via solving the Schrodinger equation.Through fitting date listed above,the spectral constants(Te,Re,ωe,ωeχe,Be,αe),which are basically consistent with the experimental results,and Franck-Condon factors of three low excited states were acquired.Simultaneously,the transition dipole moments of the A2Π-X2Σ+ electric transition of CN have been computed,deducing the radiation lifetime τ and the oscillator strength f00 of the five low vibration levels.The calculated radiation lifetime is approximately 4 μs in accordance with the experimental measurements,which helps the study of the combustion dynamic.

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中图分类号:O5612

DOI:10.3788/jqo20192502.0403

所属栏目:光与物质相互作用

基金项目:国家自然科学基金(11504256;U1610117;61573323)

收稿日期:2018-12-05

修改稿日期:2018-12-29

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阴旭梅:太原科技大学 应用科学学院,山西 太原 030024
邱选兵:太原科技大学 应用科学学院,山西 太原 030024
王高:中北大学 仪器科学与动态测试教育部重点实验室,山西 太原 030051
赖云忠:太原科技大学 应用科学学院,山西 太原 030024
和小虎:太原科技大学 应用科学学院,山西 太原 030024
魏计林:太原科技大学 应用科学学院,山西 太原 030024
李传亮:太原科技大学 应用科学学院,山西 太原 030024

联系人作者:阴旭梅(18335102894@163.com)

备注:阴旭梅(1994-),女,山西晋中人,硕士研究生,现主要从事激光光谱与应用。

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引用该论文

YIN Xu-mei,QIU Xuan-bing,WANG Gao,LAI Yun-zhong,HE Xiao-hu,WEI Ji-lin,LI Chuan-liang. Theoretical Study on Spectroscopic Properties of the Low Excited States for CN Radical[J]. Acta Sinica Quantum Optica, 2019, 25(2): 172-179

阴旭梅,邱选兵,王高,赖云忠,和小虎,魏计林,李传亮. 低激发态CN自由基光谱参数的理论研究[J]. 量子光学学报, 2019, 25(2): 172-179

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