宽带傅里叶变换微波光谱技术在络合物与化学反应研究中的应用
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摘要
基于啁啾脉冲线性调频技术的宽带微波光谱仪在测量分子转动跃迁谱线的效率上较传统的窄带光谱仪优势明显,已成为众多分子转动光谱实验室必备的实验仪器。本研究设计搭建了频率覆盖1～18 GHz的宽带傅里叶变换微波光谱仪,采用零差式检测方案并结合多脉冲自由感应衰减技术,单次扫描带宽约2 GHz。以稀释在氩气中0.5%的OCS分子为标准样品,宽带微波光谱仪同时成功检测出6种同位素异数体的分子转动跃迁信号。在此基础上,测量了Ar-OCS二元范德华络合物的分子转动光谱,并对叔丁醇与HCl的反应进行了实时监测。
Broadband microwave spectrometers based on the chirped pulse, a linear frequency modulation technology, have become indispensable experimental instruments for many rotational spectroscopy laboratories, with significant efficiency advantage in measuring molecular rotational transitions compared with traditional narrow-band spectrometers. In this work, a broadband chirped-pulse Fourier transform microwave spectrometer with frequency coverage of 1-18 GHz was designed and constructed with a single scan bandwidth about 2 GHz. The homodyne detection scheme was adopted along with the multiple FID technique applied. Using OCS molecules diluted to 0.5% in argon gas as the standard sample, rotational transitions of 6 OCS isotopologues were successfully detected by the present broadband microwave spectrometer. On this basis, the rotational spectrum of Ar-OCS van der Waals dimer was measured, and the reaction of tertiary-butyl alcohol with HCl was monitored in real time as well.
Broadband microwave spectrometers based on the chirped pulse, a linear frequency modulation technology, have become indispensable experimental instruments for many rotational spectroscopy laboratories, with significant efficiency advantage in measuring molecular rotational transitions compared with traditional narrow-band spectrometers. In this work, a broadband chirped-pulse Fourier transform microwave spectrometer with frequency coverage of 1-18 GHz was designed and constructed with a single scan bandwidth about 2 GHz. The homodyne detection scheme was adopted along with the multiple FID technique applied. Using OCS molecules diluted to 0.5% in argon gas as the standard sample, rotational transitions of 6 OCS isotopologues were successfully detected by the present broadband microwave spectrometer. On this basis, the rotational spectrum of Ar-OCS van der Waals dimer was measured, and the reaction of tertiary-butyl alcohol with HCl was monitored in real time as well.
引文
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27 https://www.nist.gov/pml/atomic-weights-and-isotopic-compositions-relative-atomic-masses
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31 Campbell E,Read W.J.Chem.Phys.,1983,78(11):6490-6501
32 Kassi S,Petitprez D,Wlodarczak G.J.Mol.Struct.,2000,517-518:375-386
2 LI Li,SUN Ming,LI Xiao-Hua,ZHAO Zhen-Wen,MA Hui-Min,GAN Hai-Yong,LIN Zhen-Hui,SHI Sheng-Cai,Ziurys L M.Chinese J.Anal.Chem.,2014,42(9):1369-1378李力,孙铭,李晓花,赵镇文,马会民,甘海勇,林镇辉,史生才,Ziurys L M.分析化学,2014,42(9):1369-1378
3 DIAO Jiang,XIE Bing.Spectrosc.Sepct.Anal.,2009,29(2):336-339刁江,谢兵.光谱学与光谱分析,2009,29(2):336-339
4 DENG Lei,ZHANG Gui-Xin,LIU Cheng,XIE Hong.Spectrosc.Sepct.Anal.,2018,38(2):627-633邓磊,张贵新,刘程,谢宏.光谱学与光谱分析,2018,38(2):627-633
5 Gordy W,Cook R.Microwave Molecular Spectra.Wiley,New York.1984:1-10
6 Townes C,Schawlow A.Microwave Spectroscopy.Dover,New York.1975:1-24
7 Ziurys L,Milam S,Apponi A,Woolf N.Nature,2007,447:1094-1097
8 Apponi A,Sun M,Halfen D,Ziurys L,Muller H.Astrophys.J.,2008,673(2):1240-1248
9 Sun M,Sargus B,Carey S,Kukolich S.J.Chem.Phys.,2015,142(15):154306
10 Sun M,Apponi A,Ziurys L.J.Chem.Phys.,2009,130(3):034309
11 Kamaee M,Sun M,Luong H,van Wijngaarden J.J.Phys.Chem.A,2015,119(41):10279-10292
12 Sun M,Kamaee M,van Wijngaarden J.J.Phys.Chem.A,2014,118(38):8730-8736
13 Gao J,Seifert N,Thomas J,Xu Y,J?ger W.J.Mol.Spectrosc.,2016,330:228-235
14 Tang J,Xu Y,McKellar A,J?ger W.Science,2002,297(5589):2030-2033
15 Dian B,Brown G,Douglass K,Pate B.Science,2008,320(5878):924-928
16 Patterson D,Schnell M,Doyle J.Nature,2013,497:475-477
17 Pate B.Science,2011,333:947-948
18 Thomas J,Seifert N,J?ger W,Xu Y.Angew.Chem.Int.Edit.,2017,56(22):6289-6293
19 Schnitzler E,Seifert N,Ghosh S,Thomas J,Xu Y,J?ger W.Phys.Chem.Chem.Phys.,2017,19(6):4440-4446
20 Thomas J,Carrillo M,Serrato III A,Lin W,J?ger W,Xu Y.J.Mol.Spectrosc.,2017,335:88-92
21 Balle T,Flygare W.Rev.Sci.Instrum.,1981,52(1):33-45
22 Brown G,Dian B,Douglass K,Geyer S,Shipman S,Pate B.Rev.Sci.Instrum.,2008,79(5):053103
23 Bird R,Pratt D.J.Mol.Spectrosc.,2011,266:81-85
24 Evangelisti L,Sedo G,van Wijngaarden J.J.Phys.Chem.A,2011,115(5):685-690
25 Wang J,Oates D,Kukolich S.J.Chem.Phys.,1973,59(10):5268-5276
26 Kubo K,Furuya T,Saito S.J.Mol.Spectrosc.,2003,222:255-262
27 https://www.nist.gov/pml/atomic-weights-and-isotopic-compositions-relative-atomic-masses
28 Shea J,Read W,Campbell E.J.Chem.Phys.,1983,79(6):2559-2568
29 Norris J,Olmsted A.Org.Synth.,1928,8:50
30 Cohen E,Drouin B,Valenzuela E,Woods R,Caminati W,Maris A,Melandri S.J.Mol.Spectrosc.,2010,260:77-83
31 Campbell E,Read W.J.Chem.Phys.,1983,78(11):6490-6501
32 Kassi S,Petitprez D,Wlodarczak G.J.Mol.Struct.,2000,517-518:375-386
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