光气的太赫兹／红外吸收及拉曼散射振动光谱研究  

The Study on the Vibrational Spectra of THz/IR Absorbance and Raman Scattering for Phosgene

作　　者：唐利斌[1,2] 姬荣斌[1] 刘树平[2] 王忆锋[1] 叶婧[2] 台国安[2] 魏长松[2] 陆志文[2] 许扬羽[2] 宋立媛[1] 陈雪梅[1] 马钰[1] 

机构地区：[1]昆明物理研究所,云南昆明650223 [2]香港理工大学,应用物理系,香港

出　　处：《红外技术》2011年第2期75-79,共5页Infrared Technology

基　　金：兵器预研项目;国防基础预研项目

摘　　要：采用Restricted Hartree-Fock(RHF)自洽场方法和密度泛函理论(DFT)方法对光气(COCl2)进行了RHF/6-31G、RHF/6-31+G、RHF/6-31++G、RHF/6-311G、RB3LYP/6-31G、RB3LYP/6-311G、RB3LYP/6-31+G、RB3LYP/6-31++G、RB3LYP/6-31G(d)、UB3LYP/6-31G十种水平上的分子结构优化、分子振动模、振动频率及强度的理论计算。研究结果表明:理论计算结果与实验数据吻合得很好,用DFT计算方法的RB3LYP/6-31G(d)基组能获得与实验结果最为接近的理论计算数据,其计算的红外频率与红外实验测试频率的相对偏差绝对值的平均值为2.43%。COCl2各种太赫兹、红外振动模的理论计算活性由大至小的顺序分别为:CCl2 a-str>CO str>CCl2 s-str>Op-deform>CO deform>CCl2 deform。COCl2各种拉曼振动模的理论计算活性由大至小的顺序分别为:CCl2 s-str>CO str>CO deform>CCl2 deform>CCl2 a-str>Op-deform。由于COCl2在9 THz有明显的THz特征吸收和拉曼散射振动,基于这一特性有望开发出毒气的太赫兹快速检测技术。The structural optimizations, molecular vibrational modes, vibrational frequencies and intensities of phosgene are calculated by using Restricted Hartree-Fock （RHF） and Density Functional Theory（DFT） at levels of RHF/6-31G, RHF/6-31＋C,RHF/6-31＋＋C, RHF/6-311, RB3LYP/6-31C, RB3LYP/6-311G, RB3LYP/6-3 I＋G, RB3LYP/6-3l＋＋G, RB3LYP/6-31G（d）, and UB3LYP/6-31G respectively. The research results show that, the theoretical calculations agree well with experimental data, and DFT RB3LYP/6-31G（d） basis set may obtain the best calculation results, the relative value of absolute deviation is 2.43% between the calculated infrared vibrational frequencies and experimental ones, the calculated activities of THz and IR vibrational modes for phosgene decrease in the sequence of CCl2 a-str〉CO str〉CC12 s-str〉Op-deform〉 CO deform〉 CCl2 deform, however, the calculated Raman intensities of the vibrational modes for phosgene are in the descending order of CC12 s-str〉CO str〉CO deform〉CC12 deform〉CC12 a-str〉Op-deform. Based on the special THz absorbance and Raman scattering of phosgene at 9 THz, a prospective fast, nondestructive poison gases THz detecting technique may be developed.

关 键 词：光气 Restricted HARTREE-FOCK 密度泛函理论 太赫兹 振动光谱 

分 类 号：TN213[电子电信—物理电子学]