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首页> 外文期刊>Journal of Molecular Spectroscopy >Applications of Fourier transform microwave (FTMW) detected infrared-microwave double-resonance spectroscopy to problems in vibrational dynamics
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Applications of Fourier transform microwave (FTMW) detected infrared-microwave double-resonance spectroscopy to problems in vibrational dynamics

机译:傅立叶变换微波(FTMW)检测到的红外-微波双共振光谱在振动动力学问题中的应用

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摘要

A description of Fourier transform microwave (FTMW) detected infrared (IR) spectroscopy is presented. A series of measurements demonstrates the versatility of using a narrowband high Q cavity FTMW spectrometer as a rotationally resolved detector for molecular-beam infrared spectroscopy. The IR-FTMW spectrometer performance is characterized by comparing the spectrum of the acetylenic C-H stretch fundamental of 1-butyne to that obtained using a high-resolution electric resonance optothermal spectrometer (EROS). Two different measurement schemes, corresponding to IR excitation before or after the microwave polarization pulse, are compared. The ability to measure rotationally resolved spectra in the region of the first overtone of the acetylenic C-H stretch is demonstrated through measurements on tertbutylacetylene and trimethylsilylacetylene. One major advantage of the current technique is that large frequency scan rates can be achieved. This feature is useful for molecules exhibiting fast intramolecular vibrational energy redistribution (IVR) as shown by measurements of the highly perturbed acetylenic C-H stretch fundamental region of cyclopropylacetylene. The second strength of the technique is that the high-sensitivity of FTMW spectroscopy makes it possible to obtain the infrared spectra of molecules in low abundance in the pulsed jet expansion. This capability is exploited to measure the infrared spectrum of the C-13 isotopomer of cyclopropylacetylene in natural abundance and to obtain the spectra of the trans and gauche conformational isomers of 4-fluorobut-1-yne. The technique is also well-suited to measuring the vibrational spectra of weakly bound complexes. The spectral simplification achieved by the double-resonance measurement has made it possible to identify weak perturbations in the acetylenic C-H stretch fundamental region of the H-C C-H-NH3 complex. The acetylenic C-H stretch fundamental spectrum of propyne-ammonia has also been obtained using the technique. (c) 2006 Elsevier Inc. All rights reserved.
机译:介绍了傅​​立叶变换微波(FTMW)检测到的红外(IR)光谱的描述。一系列测量证明了使用窄带高Q腔FTMW光谱仪作为分子束红外光谱仪的旋转分辨检测器的多功能性。 IR-FTMW光谱仪的性能是通过将1-丁炔的炔属C-H拉伸基波谱与使用高分辨率共振光热能谱仪(EROS)获得的光谱进行比较来表征的。比较了两种不同的测量方案,分别对应于微波极化脉冲之前或之后的IR激发。通过在叔丁基乙炔和三甲基甲硅烷基乙炔上的测量证明了在炔属C-H延伸的第一个泛音区域内测量旋转分辨光谱的能力。当前技术的一个主要优点是可以实现较大的频率扫描速率。此功能对于显示快速分子内振动能重新分布(IVR)的分子很有用,如对环丙基乙炔的高度扰动的炔属C-H拉伸基本区域的测量所示。该技术的第二个优势是,FTMW光谱的高灵敏度使得可以在脉冲射流扩展中获得低丰度分子的红外光谱。利用该能力以自然丰度测量环丙基乙炔的C-13异构体的红外光谱,并获得4-氟丁-1-炔的反式和gauche构象异构体的光谱。该技术也非常适合于测量弱结合复合物的振动光谱。通过双共振测量实现的光谱简化使得可以识别H-C C-H-NH3络合物的乙炔C-H拉伸基本区域中的微扰动。还使用该技术获得了炔-氨的炔属C-H拉伸基本光谱。 (c)2006 Elsevier Inc.保留所有权利。

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