An official website of the United States government
Abstract Faraday rotation spectroscopy and absorption spectroscopy are performed simultaneously in a dual comb spectroscopy arrangement with quantum cascade laser combs operating at ∼8μm. The system uses free-running laser combs that provide ∼70 cm−1spectral coverage and ∼2 MHz spectral resolution. Detection of NO2in an equilibrium mixture with N2O4and N2O is used to demonstrate selective measurements of paramagnetic NO2in the presence of spectrally interfering diamagnetic species.
more »
« less
Time-resolved HO 2 detection with Faraday rotation spectroscopy in a photolysis reactor
Faraday rotation spectroscopy (FRS) employs the Faraday effect to detect Zeeman splitting in the presence of a magnetic field. In this article, we present system design and implementation of radical sensing in a photolysis reactor using FRS. High sensitivity (100 ppb) and time resolvedin situHO2detection is enabled with a digitally balanced acquisition scheme. Specific advantages of employing FRS for sensing in such dynamic environments are examined and rigorously compared to the more established conventional laser absorption spectroscopy (LAS). Experimental results show that FRS enables HO2detection when LAS is deficient, and FRS compares favorably in terms of precision when LAS is applicable. The immunity of FRS to spectral interferences such as absorption of hydrocarbons and other diamagnetic species absorption and optical fringing are highlighted in comparison to LAS.
more »
« less
- Award ID(s):
- 1903362
- PAR ID:
- 10210160
- Publisher / Repository:
- Optical Society of America
- Date Published:
- Journal Name:
- Optics Express
- Volume:
- 29
- Issue:
- 2
- ISSN:
- 1094-4087; OPEXFF
- Format(s):
- Medium: X Size: Article No. 2769
- Size(s):
- Article No. 2769
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Electrical resistivity measurements were performed on single crystals of URu2–xOsxSi2up tox= 0.28 under hydrostatic pressure up toP= 2 GPa. As the Os concentration,x, is increased, 1) the lattice expands, creating an effective negative chemical pressurePch(x); 2) the hidden-order (HO) phase is enhanced and the system is driven toward a large-moment antiferromagnetic (LMAFM) phase; and 3) less external pressurePcis required to induce the HO→LMAFM phase transition. We compare the behavior of theT(x,P) phase boundary reported here for the URu2-xOsxSi2system with previous reports of enhanced HO in URu2Si2upon tuning withPor similarly in URu2–xFexSi2upon tuning with positivePch(x). It is noteworthy that pressure, Fe substitution, and Os substitution are the only known perturbations that enhance the HO phase and induce the first-order transition to the LMAFM phase in URu2Si2. We present a scenario in which the application of pressure or the isoelectronic substitution of Fe and Os ions for Ru results in an increase in the hybridization of the U-5f-electron and transition metald-electron states which leads to electronic instability in the paramagnetic phase and the concurrent formation of HO (and LMAFM) in URu2Si2. Calculations in the tight-binding approximation are included to determine the strength of hybridization between the U-5f-electron states and thed-electron states of Ru and its isoelectronic Fe and Os substituents in URu2Si2.more » « less
-
Abstract New particle formation (NPF) has been observed at various locations, but NPF does not occur in isoprene‐dominant forests. Recent laboratory studies were conducted to understand the role of isoprene in biogenic NPF, and these studies show that isoprene can suppress biogenic NPF, with contradicting theories. To reconcile these discrepancies, we conducted flow tube experiments of biogenic nucleation under a wide range of isoprene over monoterpene carbon ratios (R) and oxidant conditions (OH vs. ozone). Our results show isoprene either suppresses or enhances biogenic NPF, depending onRand oxidation regimes, demonstrating the synergetic effects of isoprene and HOx(OH and HO2) on biogenic NPF. Whereas the suppression of NPF by isoprene is due to the product suppression effects of monoterpene dimers (C20), RO2 + HO2termination reactions also play important roles in suppressing the dimer formation, another likely process to suppress NPF in the atmosphere.more » « less
-
Abstract Control of surface functionalization of MXenes holds great potential, and in particular, may lead to tuning of magnetic and electronic order in the recently reported magnetic Cr2TiC2Tx. Here, vacuum annealing experiments of Cr2TiC2Txare reported with in situ electron energy loss spectroscopy and novel in situ Cr K‐edge extended energy loss fine structure analysis, which directly tracks the evolution of the MXene surface coordination environment. These in situ probes are accompanied by benchmarking synchrotron X‐ray absorption fine structure measurements and density functional theory calculations. With the etching method used here, the MXene has an initial termination chemistry of Cr2TiC2O1.3F0.8. Annealing to 600 °C results in the complete loss of F, but O termination is thermally stable up to (at least) 700 °C. These findings demonstrate thermal control of F termination in Cr2TiC2Txand offer a first step toward termination engineering this MXene for magnetic applications. Moreover, this work demonstrates high energy electron spectroscopy as a powerful approach for surface characterization in 2D materials.more » « less
-
Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li+mobility. In this study, Li+transport in structurally modified Li3HoCl6, via Br−introduction and Li+deficiency, is explored. The optimized Li3‐3yHo1+yCl6‐xBrxachieves an ionic conductivity of 3.8 mS cm−1at 25 °C, the highest reported for holmium halide materials.6,7Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li+motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li+migration. Bond valence site energy analysis highlights preferred Li+transport pathways, particularly in structural planes devoid of Ho3+blocking effects. Molecular dynamics simulations corroborate enhanced Li+diffusion with Br−introduction into Li3HoCl6. Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li+diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li+motion and exchange between the 2d and 4h sites. Li3‐3yHo1+yCl6‐xBrxalso demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries.more » « less
