Inelastic x-ray scattering spectra excited at the 1s(-1)π* resonance of gas phase O2 have been recorded with an overall energy resolution that allows for well-resolved vibrational progressions. The nuclear wave packet dynamics in the intermediate state is reflected in vibrational excitations of the electronic ground state, and by fine-tuning the excitation energy the dissociation dynamics in the predissociative B'(3)Πg final state is controlled.
Resonant inelastic x-ray scattering spectra excited at the O1s −1 π * resonance of liquid acetone are presented. Scattering to the electronic ground state shows a resolved vibrational progression where the dominant contribution is due to the C-O stretching mode, thus demonstrating a unique sensitivity of the method to the local potential energy surface in complex molecular systems. For scattering to electronically excited states, soft vibrational modes and, to a smaller extent, intermolecular interactions give a broadening, which blurs the vibrational fine structure. It is predicted that environmental broadening is dominant in aqueous acetone.
Stripline split-ring resonator with integrated optogalvanic sample cell.Laser Physics Letters, 11(4) dating and pharmaceutical sciences. However, recent reports show that ICOGS suffers from substantial problems with reproducibility. To qualify ICOGS as an analytical method, more stable and reliable plasma generation and signal detection are needed. In our proposed setup, critical parameters have been improved. We have utilized a stripline split-ring resonator microwave-induced microplasma source to excite and sustain the plasma. Such a microplasma source offers several advantages over conventional ICOGS plasma sources. For example, the stripline split-ring resonator concept employs separated plasma generation and signal detection, which enables sensitive detection at stable plasma conditions. The concept also permits in situ observation of the discharge conditions, which was found to improve reproducibility. Unique to the stripline split-ring resonator microplasma source of in this study, is that the optogalvanic sample cell has been embedded in the device itself. This integration enabled improved temperature control and more stable and accurate signal detection. Significant improvements are demonstrated, including reproducibility, signal-to-noise ratio and precision.
Abstract. In this paper, a stripline split-ring resonator microwave-induced plasma source, aimed for integration in complex systems, is presented and compared with a traditional microstrip design. Devices based on the two designs are evaluated using a plasma breakdown test setup for measuring the power required to ignite plasmas at different pressures. Moreover, the radiation efficiency of the devices is investigated with a Wheeler cap, and their electromagnetic compatibility is investigated in a variable electrical environment emulating an application. Finally, the basic properties of the plasma in the two designs are investigated in terms of electron temperature, plasma potential, and ion density. The study shows that, with a minor increase in plasma ignition power, the stripline design provides a more isolated and easy-to-integrate alternative to the conventional microstrip design. Moreover, the stripline devices showed a decreased antenna efficiency as compared to their microstrip counterparts, which is beneficial for plasma sources. Furthermore, the investigated stripline devices exhibited virtually no frequency shift in a varying electromagnetic environment, whereas the resonance frequency of their microstrip counterparts shifted up to 17.5%. With regards to the plasma parameters, the different designs showed only minor differences in electron temperature, whereas the ion density was higher with the stripline design.Keywords: Split-ring resonator, Microwave plasma, Microstrip, Stripline, Plasma, Wheeler cap, Langmuir probe
Optogalvanic detectors show great potential for infrared spectroscopy, especially in cavity enhanced techniques where they, in contrast to ordinary absorption detectors, can perform intracavity measurements. This enables them to utilize the signal-to-noise ratio improvement gained from the extended effective path length inside an optical cavity, without losing signal strength due to the limited amount of light exiting through the rear mirror.However, if optogalvanic detectors are to become truly competitive, their intrinsic sensitivity and stability has to be improved. This, in turn, requires a better understanding of the mechanisms behind the generation of the optogalvanic signal. The study presented here focuses on an optogalvanic detector based on a miniaturized stripline split-ring resonator plasma source equipped with Langmuir probes for detecting the optogalvanic signal. In particular, the effect of applying a constant bias voltage to one of the probes is investigated, both with respect to the sensitivity and stability, and to the mechanism behind the generation of the signal. Experiments with different bias voltages at different pressures and gas composition have been conducted. In particular, two different gas compositions (pure CO 2 and 0.25% CO 2 in 99.75% N 2 ) at six different pressures (100 Pa to 600 Pa) have been studied. It has been shown that probe biasing effectively improves the performance of the detector, by increasing the amplitude of the signal linearly over one order of magnitude, and the stability by about 40% compared with previous studies. Furthermore, it has been shown that relatively straightforward plasma theory can be applied to interpret the mechanism behind the generation of the signal, although additional mechanisms, such as rovibrational excitation from electron-molecule collisions, become apparent in CO 2 plasmas with electron energies in the 1-6 eV range. With the achieved performance improvement and the more solid theoretical framework presented here, stripline split-ring resonator optogalvanic detectors can evolve into a compact, inexpensive and easy-to-operate alternative for future infrared spectrometers.
The demand for analysis of smaller samples in isotopic ratio measurements of rare isotopes is continuously rising with the development of new applications, particularly in biomedicine. Interesting in this aspect are methods based on optogalvanic spectroscopy, which have been reported to facilitate both 13 C-to-12 C and 14 C-to-12 C ratio measurements with high sensitivity. These methods also facilitate analysis of very small samples, down to the microgram range, which makes them very competitive to other technologies, e.g., accelerator mass spectroscopy. However, there exists a demand for moving beyond the microgram range, especially from regenerative medicine, where samples consist of, e.g., DNA, and, hence, the total sample amount is extremely small. Making optogalvanic spectroscopy of carbon isotopes applicable to such small samples, requires miniaturization of the key component of the system, namely the plasma source, in which the sample is ionized before analysis. In this paper, a novel design of such a microplasma source based on a stripline split-ring resonator is presented and evaluated in a basic optogalvanic spectrometer. The investigations focus on the capability of the plasma source to measure the optogalvanic signal in general, and the effect of different system and device specific parameters on the amplitude and stability of the optogalvanic signal in particular. Different sources of noise and instabilities are identified, and methods of mitigating these issues are discussed. Finally, the ability of the cell to handle analysis of samples down to the nanogram range is investigated, pinpointing the great prospects of stripline split-ring resonators in optogalvanic spectroscopy. V C 2013 AIP Publishing LLC. [http://dx
The present paper describes a system and method for indirect emission spectroscopy of CO2 in the visible spectrum. This is achieved by using a microplasma spectrometer that first converts CO2 into CO and then measures emissions from the CO Ångström system (B1Σ + → A1Π) at 560 nm. The experiments were performed on gaseous samples of CO2, mixed in both N2 and air, to concentrations between 0.01% and 100%. In addition to the microplasma spectrometer, the process was monitored by mass spectrometry with a residual gas analyzer. The CO2 to CO conversion efficiency was found to be very high, reaching a maximum of 41% at close to 100% selectivity. Furthermore, the CO Ångström system was shown to facilitate excellent spectroscopic measurement of CO2 concentrations below 10%, with a linearity of R2 > 0.99 and an expected limit of detection in the parts-per-thousands range. The most promising aspect of the results was that the analysis was performed on extremely small total sample amounts where the gas flow through the systems was in the 0.1 µmole/s range. Hence, the present system has the prospect of filling a void in current sensor technology, where inexpensive and easy-to-use optical systems, such as nondispersive infrared sensors, cannot handle small sample amounts, while mass spectrometers, which can handle such samples, still are expensive, complex, and bulky.
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