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本文在采用乘积近似方法计算二氧化碳、一氧化碳分子总的配分函数(其中分子的振动配分函数采用谐振子近似, 转动配分函数采用非刚性转子模型, 并考虑了离心扭曲修正)的基础上, 利用所得配分函数和振动跃迁矩平方的实验值以及Herman-Wallis系数, 计算了1.5 μm 附近二氧化碳30012–00001跃迁带和一氧化碳3–0跃迁带在300–6000 K温度范围内部分温度下的吸收线强; 为验证计算方法和结果的准确性, 在基于可调谐二极管激光吸收光谱技术搭建的高温测量系统中, 对300–800 K温度范围内部分谱线线强进行了测量, 并把计算结果、测量结果及HITRAN数据库中对应数据进行了对比, 发现相对偏差小于3%, 证明了本方法的有效性, 同时计算及测量所得高温线强数据可对HITRAN数据库进行有效的校正和补充.
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关键词:
- 二氧化碳和一氧化碳 /
- 配分函数 /
- 高温光谱 /
- 可调谐二极管激光吸收光谱
Accurate spectroscopic parameters of probed species, especially the line strengths at high temperatures, are important for combustion diagnosis based on tunable diode laser absorption spectroscopy (TDLAS). However, most of the line strengths in databases are measured at normal atmospheric temperature and calculated at high temperatures. For example, the mostly used HITRAN database focuses on atmospheric conditions where the temperature ranging from 200-350 K. The high-temperature parameters in HITRAN database are obtained by calculation and the temperatures are limited to 3000 K. In this paper the line strengths of 30012-00001 transition band of CO2 and 3-0 transition band of CO at normal temperature (300 K) and some high temperatures (400-6000 K) are calculated using our calculated partition function and experimental transition moment squared and Herman-Waills factor coefficients. The total internal partition sums (TIPS) are calculated for CO2 and CO with the product approximation of the vibrational and the rotational partition functions. The vibrational partition function is calculated in harmonic oscillator approximation. For rotational partition sums, the centrifugal distortion corrections are taken into consideration. In order to validate the calculation, a high-temperature measurement system based on TDLAS is developed using a DFB diode laser near 1.573 μm. High-resolution absorption spectra of CO2 and CO can be recorded in a heated cell as a function of temperature and pressure. The 9 lines of CO2 30012-00001 band and 2 lines of CO 3-0 band have been measured by means of direct absorption spectroscopy in the temperature range of 300-800 K. The corresponding line strengths are inferred from the measured direct absorption spectrum. The calculated result and experimental data are compared with the HITRAN values. The calculated and measured data agree well with the existing databases (HITRAN 2012), the discrepancies being less than 3% for most of the probed transitions. All the results confirm the validity of the calculation of total partition function and the line strengths calculated. The variation of the line strength as a function of temperature for a certain transition is also discussed. While the lower state energy determines the equilibrium molecular population in the unabsorbing state as a function of temperature, how the line strength of a particular transition varies with temperature can also be controlled.-
Keywords:
- CO2 and CO /
- partition function /
- high temperature spectrum /
- tunable diode laser absorption spectroscopy (TDLAS)
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[8] Predoi-Cross A, Liu W, Murphy R, Povey C, Gamache RR, Laraia A L, McKellar A RW, Hurtmans D R, Devi V M 2010 J. Quant. Spectrosc. Radiat. Transfer 111 1065
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[15] Song X S, Yang X D, Guo Y D, Wang J, Cheng X L, Ling-Hu L F 2007 Commun. Theor. Phys. 47 892
[16] Rothman L S, Gordon I E, Babikov Y, Barbe A, Benner D C, Bernath PF, Birk M, Bizzocchi L, Boudon V, Brown L R, Campargue A, Chance K, Cohen E A, Coudert L H, Devi V M, Drouin B J, Fayt A, Flaud J M, Gamache RR, Harrison J J, Hartmann J, Hill C, Hodges J T, Jacquemart D, Jolly A, Lamouroux J, Roy RJ L, Li G, Long D A, Lyulin O M, Mackie C J, Massie S T, Mikhailenko S, Mller H S P, Naumenko O V, Nikitin A V, Orphal J, Perevalov V, Perrin A, Polovtseva E R, Richard C, Smith M A H, Starikova E, Sung K, Tashkun S, Tennyson J, Toon G C, Tyuterev V G, Wagner G 2013 J. Quant. Spectrosc. Radiat. Transfer 130 4
[17] Chen W D, Kosterev A A, Tittel F K, Gao X M, Zhao W X 2008 Appl. Phys. B 90 311
[18] Xia H, Dong F Z, Wu B, Zhang Z R, Pang T, Sun PS, Cui X J, Han L, Wang Y 2015 Chin. Phys. B 24 034204
[19] Che L, Ding Y J, Peng Z M, Li X H 2012 Chin. Phys. B 21 127803
[20] Gamache RR, Kennedy S, Hawkins R, Rothman L S 2000 J. Mol. Struct. 517 407
[21] Herzberg G 1947 Molecular Spectra and Molecular StructureII. Infrared and Raman Spectra of Polyatomic Molecules (New York: Van Nostrand) p76
[22] Norton RH, Rinsland C P 1991 Appl. Opt. 30 389
[23] McDowell RS 1988 J. Chem. Phys. 88 356
[24] Song X S, Ling-Hu RF, Li D H, Yan A Y 2007 Chin J. At. Mol. Phys.24 647
[25] Song X S, Cheng X L, Yang X D, Ling-Hu RF 2007 Acta Phys. Sin. 56 4428 (in Chinese) [宋晓书, 程新路, 杨向东, 令狐荣锋 2007 56 4428]
[26] Rachet F, Margottinmaclou M, Elazizi M, Henry A, Valentin A 1994 J. Mol. Spectrosc. 164 196
[27] Liu X 2006 Ph. D. Dissertation (California: Stanford University)
-
[1] Banwell C N, Mccash E M 1994 Fundamentals of Molecular Spectroscopy (4th edition)(New York: McGraw-Hill Higher Education) p21
[2] Guelachvili G 1979 J. Mol. Spectrosc. 75 251
[3] Picqué N, Guelachvili G, Dana V, Mandin J Y 2000 J. Mol. Struct. 517 427
[4] Chackerian C, Freedman R., Giver L P, Brown L R 2001 J. Mol. Spectrosc. 210 119
[5] Ogilvie J F, Cheah S L, Lee Y P, Sauer S P2002 Theor. Chem. Acc. 108 85
[6] Campargue A, Karlovets E V, Kassi S 2015 J. Quant. Spectrosc. Radiat. Transfer 154 113
[7] Lamouroux J, Gamache RR, Laraia A L, Hartmann J, Boulet C 2012 J. Quant. Spectrosc. Radiat.Transfer 113 991
[8] Predoi-Cross A, Liu W, Murphy R, Povey C, Gamache RR, Laraia A L, McKellar A RW, Hurtmans D R, Devi V M 2010 J. Quant. Spectrosc. Radiat. Transfer 111 1065
[9] Toth RA, Hunt RH, Plyler E K 1971 J. Mol. Spectrosc. 38 107
[10] Boudjaadar D, Mandin J Y, Dana V, Picqué N, Guelachvili G 2006 J. Mol. Spectrosc. 236 158
[11] Miller C E, Brown L R 2004 J. Mol. Spectrosc. 228 329
[12] Teffo J L, Claveau C, Valentin A 1998 J. Quant. Spectrosc. Radiat. Transfer 59 151
[13] Claveau C, Teffo J L, Hurtmans D, Valentin A 1998 J. Mol. Spectrosc. 189 153
[14] Toth RA, Brown L R, Miller C E, Devi V M, Benner D C 2006 J. Mol. Spectrosc. 239 221
[15] Song X S, Yang X D, Guo Y D, Wang J, Cheng X L, Ling-Hu L F 2007 Commun. Theor. Phys. 47 892
[16] Rothman L S, Gordon I E, Babikov Y, Barbe A, Benner D C, Bernath PF, Birk M, Bizzocchi L, Boudon V, Brown L R, Campargue A, Chance K, Cohen E A, Coudert L H, Devi V M, Drouin B J, Fayt A, Flaud J M, Gamache RR, Harrison J J, Hartmann J, Hill C, Hodges J T, Jacquemart D, Jolly A, Lamouroux J, Roy RJ L, Li G, Long D A, Lyulin O M, Mackie C J, Massie S T, Mikhailenko S, Mller H S P, Naumenko O V, Nikitin A V, Orphal J, Perevalov V, Perrin A, Polovtseva E R, Richard C, Smith M A H, Starikova E, Sung K, Tashkun S, Tennyson J, Toon G C, Tyuterev V G, Wagner G 2013 J. Quant. Spectrosc. Radiat. Transfer 130 4
[17] Chen W D, Kosterev A A, Tittel F K, Gao X M, Zhao W X 2008 Appl. Phys. B 90 311
[18] Xia H, Dong F Z, Wu B, Zhang Z R, Pang T, Sun PS, Cui X J, Han L, Wang Y 2015 Chin. Phys. B 24 034204
[19] Che L, Ding Y J, Peng Z M, Li X H 2012 Chin. Phys. B 21 127803
[20] Gamache RR, Kennedy S, Hawkins R, Rothman L S 2000 J. Mol. Struct. 517 407
[21] Herzberg G 1947 Molecular Spectra and Molecular StructureII. Infrared and Raman Spectra of Polyatomic Molecules (New York: Van Nostrand) p76
[22] Norton RH, Rinsland C P 1991 Appl. Opt. 30 389
[23] McDowell RS 1988 J. Chem. Phys. 88 356
[24] Song X S, Ling-Hu RF, Li D H, Yan A Y 2007 Chin J. At. Mol. Phys.24 647
[25] Song X S, Cheng X L, Yang X D, Ling-Hu RF 2007 Acta Phys. Sin. 56 4428 (in Chinese) [宋晓书, 程新路, 杨向东, 令狐荣锋 2007 56 4428]
[26] Rachet F, Margottinmaclou M, Elazizi M, Henry A, Valentin A 1994 J. Mol. Spectrosc. 164 196
[27] Liu X 2006 Ph. D. Dissertation (California: Stanford University)
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