HCl气体高分辨红外发射光谱的研究
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摘要
利用超高分辨傅里叶变换红外光谱仪对HCl气体的红外发射光谱进行了测量,并与基于第一性原理的分子动力学方法计算出的分子振动谱的结果进行了对比分析.结果表明,分子动力学计算得到的振动谱和实验得到的红外谱线的包络符合得很好,特别是对HCl振动谱带边缘各峰值位置的计算结果与实验符合较好.但对谱带中部各峰值位置的计算结果与实验有一定偏差.另外,对于HCl振动谱带的两个分支内各自最大强度所处位置的计算结果偏小;对各分支积分能量的计算结果与实验数据不符,其中右侧分支(较大波数分支)积分能量的计算结果偏大.因此,分子动力学算法应用于气体红外光谱的计算时虽然能与实验基本符合,但是和精细谱比对还有待进一步改进.
The infrared emission spectra of HCl gas were measured by high-resolution Fourier transform infrared spectrometer,and compared with the results of vibrational spectra calculated by first-principles molecular dynamics.The results show that the envelope of the calculated and measured infrared spectrum agrees well with each other.Especially,for each peak position at the edge of the HCl vibration band,the calculated spectrum is in accord with the experiments,but each calculated peak position in the middle of the band deviates from the experimental result.In addition,for the two branches of the HCl vibration band,the calculated maximum strength in each branch is small.The calculated integral energy of each branch is inconsistent with the experimental data,and the calculated integral energy of the right branch(the branch with larger wave number)is large.Therefore,the calculation of vibrational spectrum based on molecular dynamics agrees with the measurements,though it should be improved when it is compared with the high-resolution infrared spectrum of gas.
The infrared emission spectra of HCl gas were measured by high-resolution Fourier transform infrared spectrometer,and compared with the results of vibrational spectra calculated by first-principles molecular dynamics.The results show that the envelope of the calculated and measured infrared spectrum agrees well with each other.Especially,for each peak position at the edge of the HCl vibration band,the calculated spectrum is in accord with the experiments,but each calculated peak position in the middle of the band deviates from the experimental result.In addition,for the two branches of the HCl vibration band,the calculated maximum strength in each branch is small.The calculated integral energy of each branch is inconsistent with the experimental data,and the calculated integral energy of the right branch(the branch with larger wave number)is large.Therefore,the calculation of vibrational spectrum based on molecular dynamics agrees with the measurements,though it should be improved when it is compared with the high-resolution infrared spectrum of gas.
引文
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[2]罗伟琪.振动光谱技术用于食品分析的研究[D].长沙:湖南大学,2011.
[3]徐亮,刘建国,高闽光,等.FTIR监测北京地区CO2和CH4及其变化分析[J].光谱学与光谱分析,2007,27(5):889-891.
[4]张衍国,邓高峰,郭亮,等.废弃物焚烧产物中HCl的检测研究[J].安全与环境学报,2002,2(2):7-9.
[5]万敏,冷杰,杨锐,等.尾焰红外辐射的光谱特性及空间分布特性的计算[C].第十七届全国激光学术会议.
[6]张术坤,蔡静.尾焰红外辐射特性计算研究综述[J].激光与红外,2010,40(12):1277-1282.
[7]文玉华,朱如曾,周富信,等.分子动力学模拟的主要技术[J].力学进展,2003,33(1):65-73.
[8]Kresse G,Furthmuller J.Efficient iterative schemes for ab initio total-energy calculations using aplanewave basis set[J].Phys Rev B,1996,54(16):11169.
[9]Kresse G,Furthmuller J.Efficiency of ab-initio total energy calculations for metals and semiconductors using aplane-wave basis set[J].Comput Mater Sci,1996,6(1):15-50.