Doppler-free infrared spectroscopy by opto-thermal detection

该提案中描述的原始项目是利用色心激光器构建高分辨率光谱仪，但由于激光器的致命损坏而变得不切实际。相反，我们进行了以下高分辨率光谱研究符合相同的目的。首先，我们构建了一个高分辨率LIF光谱仪。用一个装有脉冲超声喷嘴的样品池对NeBr_2的货车范德华络合物的B - X带进行了观测。通过<-1>使用带有脉冲放电喷嘴的池，以0.028 cm ↑ [2]的分辨率观察OH自由基的A^2 π-X^2Π带，进一步验证了这一点。第二，我们发展了一种新的光谱技术，其中毫米波光谱、脉冲超声射流和准分子激光光解结合在一起。 ...更多信息 是的。这种技术被应用于乙烯基自由基光谱的观察。该自由基的面内CH弯曲振动受双最小势支配，基态振动分裂为“s”和“a”隧穿二重态。我们观察到连接“s”和“a”状态的隧道旋转跃迁，以及发生在“s”或“a”状态内的纯旋转跃迁。对双最小势能、电子-自旋-转动相互作用、电子-自旋-核-自旋相互作用有了精确的认识。第三，我们利用红外半导体激光光谱结合准分子激光光解技术，观测到了CoCO自由基的高分辨振转光谱。CO伸缩振动（ν_1）的基频带，以及弯曲振动（ν_2）和CoO伸缩振动（ν_3）激发态的热带。获得了关于平衡结构和其他方面的精确知识。证实了该自由基具有^2Δ i电子基态。毫米波光谱也被观察到产生精确的超精细相互作用常数的Co核。少

The original project described in the proposal was to construct an apparatus for high-resolution spectroscopy utilizing a color-center laser, but became impracticable because of a fatal damage of the laser. Instead, we carried out the following high-resolution spectroscopic studies in line with the same purpose.First, we constructed an apparatus for high-resolution LIF spectroscopy. The apparatus was tested by the observation of the B - X band of the NeBr_2 van der Waals complex using a cell with a pulsed supersonic nozzle. It was further tested by the observation at a resolution of 0.028 cm^<-1> of the A^2Σ-X^2Π band of the OH radical using a cell with a pulsed discharge nozzle. We hope that this apparatus may be developed for application to double resonance spectroscopy in which microwave and cavity ringdown techniques are combined.Second, we have developed a new spectroscopic technique in which millimeter wave spectroscopy, pulsed supersonic jet, and excimer laser photolysis were co … More mbined. This technique was applied to observation of the spectrum of the vinyl radical. The in-plane CH bending vibration of this radical is governed by a double minimum potential, and the ground vibrational state is split into the "s" and "a" tunneling doublet. We observed tunneling-rotation transitions connecting the "s" and "a" states, as well as pure rotational transitions which occur within the "s" or "a" state. Precise knowledge on the double minimum potential, electron-spin-rotation interaction, electron-spin-nuclear-spin interactions.Third, we observed the high-resolution vibration-rotation spectrum of the CoCO radical by infrared diode laser spectroscopy combined with excimer laser photolysis. The fundamental band of the CO stretching (ν_1) vibration, and hot bands starting from excited states of the bending (ν_2) and CoO stretching (ν_3) vibrations. Precise knowledge was obtained on the equilibrium structure and others. It was confirmed that this radical has the ^2Δ_i, electronic ground state. Millimeter wave spectrum was also observed yielding precise hyperfine interaction constants of the Co nucleus. Less