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Results for “Gas phase laser spectroscopy”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Application of deep learning to single-shot gas-phase laser-induced breakdown spectroscopy

Single-shot fs laser-induced breakdown spectroscopy (LIBS) has the potential to capture ns-scale electrode desorption phenomena in pulsed power fusion drivers. However, the successful implementation of the diagnostic for this purpose is challenging, as it requires interpreting single-shot measurements collected from low-density gas mixtures. In this work, we demonstrate the efficacy of a Bayesian-optimized convolutional neural network (CNN) to interpret these measurements. We generated 256 distinct measurement conditions at relevant gas pressures ranging from 80–530 mTorr by mixing 100–250 sccm H 2 and 50–200 sccm CH 4 in increments of 10 sccm. Despite the considerable overlap between signals separated by 20 sccm, the CNN is able to predict the H 2 flow rate with a root-mean-square error (RMSE) of 15.9 sccm and the CH 4 flow rate with an RMSE of 12.0 sccm. The average relative prediction error is <9% for each gas and largely remains below or near 10%.

Brown, Nathan Parnell [Sandia National Lab. (SNL-N↗
DOE OSTI2025

Coupling to rotational manifolds to improve gas-phase pump–probe spectroscopic models

The physical picture of gas-phase optical transitions is normally presented as an isolated two-level system balanced by upward and downward processes. Isolated models assume a phenomenological treatment of collisional dephasing but do not strictly account for collisional population exchange with the rotational baths. While this assumption is valid under low-intensity conditions, where excitation is rate-limiting, isolated models can deviate from Beer’s Law at sufficient pressures and monochromatic intensities when both collisional broadening and power broadening are comparable to (or greater than) lifetime broadening, which are not uncommon conditions for cavity enhanced spectroscopies in the mid-IR spectral range. Although this problem has been addressed by rate-equation models for linear absorption measurements, a general treatment for multi-level quantum mechanical models suitable for non-linear absorption measurements (two-photon/two-color/pump–probe) is lacking. Isolated models require physical parameter inputs that disagree with expected values by at least an order of magnitude. These non-physical models undermine the ability to predict non-linear signal strengths under untested conditions and thereby limit the potential to optimize the sensitivity of non-linear spectroscopies and to expand their analytical applications (e.g., new analytes and/or buffer gases, changes in cavity free-spectral-range, changes in intracavity powers or wavelengths, and accurate investigation of physical phenomena). In this study, we derive bath-coupled models for gaseous pump–probe spectroscopy by application of the quantum Lindblad equation and detailed balance. Bath-coupled models are shown to fit data consistently across variations in intensity and agree with all physically expected values.

Cavity ring-down spectroscopy↗
DOE OSTI2024

Predissociation-based measurements of bond dissociation energies: US 2 , OUS, and USe

The uranium-containing molecules US 2 , OUS, and USe have been investigated using a pulsed laser ablation supersonic beam molecular source with time-of-flight mass spectrometric detection. Spectra have been recorded using the resonant two-photon ionization method over the spectroscopic range from 277 to 238 nm. These species have a myriad of excited electronic states in this spectroscopic region, leading to spectra that are highly congested and appear quasicontinuous. Sharp predissociation thresholds are observed, allowing precise bond dissociation energies to be measured. In the case of the triatomic molecules, it was necessary to use one laser for excitation and a delayed laser for ionization in order to observe a sharp predissociation threshold that allowed a precise bond dissociation energy to be measured. The resulting thermochemical values are D 0 (SU-S) = 4.910 ± 0.003 eV, D 0 (OU-S) = 5.035 ± 0.004 eV, and D 0 (USe) = 4.609 ± 0.009 eV. These results provide the first measurement of D 0 (USe) and reduce the error limits in the previous values of D 0 (SU-S) and D 0 (OU-S) by a factor of more than 70.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Plasma Assisted Combustion and Chemical Processing: Chapter 9 - Plasma Diagnostics

Plasma dynamics and chemistry have a broad range of timescales from picoseconds to milliseconds. In addition, it involves nonequilibrium energy transfer between electrons, ions, electronically and vibrationally excited states, radicals, intermediate species, and reactants and products as well as surface charges and chemistry. To understand plasma physics and chemistry, it is essential to conduct time and space resolved, quantitative detection of nonequilibrium temperature distributions, electron energy and number density, electric field, and species concentrations. There are enormous publications and review articles on this subject. The focus of this chapter is to be placed on the most recent progress in gas phase plasma properties and chemistry, especially on optical emission spectroscopy, laser absorption spectroscopy, Faraday rotational spectroscopy, Raman and Thompson scattering, femtosecond and picosecond (fs/ps) coherent anti-Stokes Raman scattering (CARS) spectroscopy, and electric field-induced second harmonic generation methods.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Quantification of trace iodine using laser-induced breakdown spectroscopy for real-time monitoring of nuclear off-gas streams

This study evaluated the potential of laser-induced breakdown spectroscopy (LIBS) for real-time monitoring of trace gas-phase iodine, which is an element of high significance in nuclear applications due to its long radioactive half-life (as iodine-129), volatility, and biological impact. In anticipation of iodine evolving into off-gas systems in molten salt reactor and nuclear fuel recycling applications, this research aimed to assess LIBS performance in flowing argon and helium matrices; optimize measurement parameters using a multichannel spectrometer; and perform calibrations to assess predictive capabilities and limits of detection (LODs). Experimental results successfully measured gas-phase iodine in flowing argon and helium; however, trace iodine was not detected in air. Optimal delay times were determined to be 10 µs for argon and 1 µs for helium, which are consistent with the expected shorter plasma lifetime in helium relative to argon. An emission line survey was provided with the 206.16, 804.37, 902.24, and 905.83 nm peaks, which were identified as the strongest emission peaks. Calibration models were successfully built in both helium and argon, achieving LODs down to 3 ppm in helium and 5 ppm in argon. The iodine emission at 905.83 nm emerged as the most robust for calibration and was subsequently applied to a time series dataset in argon. The predictive trace confirmed the feasibility of employing LIBS for continuous, online quantification of trace iodine in flowing gas systems.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗
DOE OSTI2025

Activation, Dehydrogenation, and Carbon–Carbon Coupling of Methane by Iridium Cations Studied by Infrared Multiple Photon Dissociation Spectroscopy and Density Functional Theory

Products resulting from the sequential activation of one, two, three, and four methane molecules by atomic iridium cations were characterized by gas-phase infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. Iridium cations were generated using a laser ablation source and reacted with methane in a linear radiofrequency ion trap before mass analysis and spectroscopic interrogation in a Fourier transform ion cyclotron resonance mass spectrometer coupled to the free-electron laser for intracavity experiments (FELICE) beamline. Product ions were irradiated using infrared light over the 250–1500 cm –1 range. Comparisons between the experimental and DFT-calculated spectra enabled structural determination of the products formed. The observed products include HIrCH + , Ir(CH 2 ) 2 + , H s Ir(C 3 H 5 ) + , and Ir(CH 3 ) s (C 3 H 5 ) + , where the subscript s denotes a syn orientation of the two ligands. Furthermore, formation of the latter two products provides evidence for efficient C–H bond activation and subsequent C–C coupling on the atomic iridium cation.

Chemical reactions↗
DOE OSTI2025

Molecular axis distribution moments in ultrafast transient absorption spectroscopy: A path toward ultrafast quantum state tomography

In ultrafast time-resolved experiments with gas phase molecules, the alignment of the molecular axis relative to the polarization of the interacting laser pulses plays a crucial role in determining the dynamics following this light–matter interaction. The molecular axis distribution is influenced by the interacting pulses and is intrinsically linked to the electronic coherences of the excited molecules. However, in typical theoretical calculations of such interactions, the signal is either calculated for a single molecule in the molecular frame or averaged over all possible molecular orientations to compare with the experiment. Such averaging removes information about anisotropy in the molecular-axis distribution, even though anisotropic contributions can play a significant role in the measured experimental signal. Here, we calculate the laboratory frame transient electronic first-order polarization [P (1) ] spectra in terms of separated molecular frame and laboratory frame quantities. The laboratory frame polarizations are compared with orientation-averaged quantum master equation calculations, demonstrating that orientation-averaging captures only the isotropic contributions. We show that our formalism also allows us to evaluate the anisotropic contributions to the spectrum. Lastly, we discuss the application of this approach to achieve ultrafast quantum state tomography using transient absorption spectroscopy and field observables in nonlinear spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Evolution and persistence of SiO emission in nanosecond laser ablation plumes

Analyzing laser-produced plasmas in a controlled oxygen-containing environment provides insight into the formation and evolution of molecular species through gas-phase oxidation. This study explores the role of ambient pressure and oxygen availability in forming SiO molecular species in laser ablation plumes. The self-emission emanating during the reactive ablation of Si targets was characterized by optical emission spectroscopy and optical time-of-flight techniques. Our results showed that the SiO species formation was greatly influenced by both the ambient pressure and oxygen availability. The intensity and the persistence of SiO emission bands are lower at higher oxygen concentrations, indicating they are depopulated by the formation of more complex silicon oxides. The oxygen partial pressure effects on plume chemistry showed that SiO formation is favored even with a minimal oxygen concentration in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Real-time monitoring of trace noble gases using laser-induced breakdown spectroscopy—An investigation of the impact of bulk gas on plasma properties and sensitivity

The impact of Ar and He bulk gases on laser-induced breakdown spectroscopy (LIBS) real-time monitoring of trace Xe and Kr was assessed. LIBS is being developed as a monitoring tool for measuring noble gas transport in molten salt systems, in which traditional sensors may face challenges associated with radiation, corrosive materials, and/or mixed phases. The plasma temperature and electron densities of LIBS plasmas were measured in both static and various flowing Ar and He streams (0–5 L min −1 ). The use of an Ar bulk gas resulted in higher plasma temperature, greater electron densities by an order of magnitude, and extended plasma lifetime compared with when He bulk gas was used. Gas flow rate was found to have little impact on plasma temperature; however, its effect on electron density was significant, indicating the need to consider flow rate–specific models. Matrix effects on emission peaks were reported for both bulk gases. Due to these matrix effects, multivariate models were developed for Xe and Kr ranging from 0 to 700 ppm in both bulk gases. Although the predictive behavior was similar (root mean square error of prediction ranging from 11.1 to 20.6 ppm), the limits of detection were superior in He (Xe: 22.9 ppm, Kr: 30.4 ppm). Furthermore, these models were employed in demonstrative real-time tests (>1 h), which showed strong predictive precision (relative standard deviation <5 %) regardless of the bulk gas. Ultimately, this study provides a guide for the considerations required when developing gaseous LIBS models for real-time monitoring.

Gas flow effects↗
DOE OSTI2024

Ion Manipulation from Liquid Xe to Vacuum: Ba-Tagging for a nEXO Upgrade and Future 0 νββ Experiments

Neutrinoless double beta decay (0𝜈𝛽𝛽) provides a way to probe physics beyond the Standard Model of particle physics. The upcoming nEXO experiment will search for 0𝜈𝛽𝛽 decay in 136 Xe with a projected half-life sensitivity exceeding 10 28 years at the 90% confidence level using a liquid xenon (LXe) Time Projection Chamber (TPC) filled with 5 tonnes of Xe enriched to ∼90% in the 𝛽𝛽-decaying isotope 136 Xe. In parallel, a potential future upgrade to nEXO is being investigated with the aim to further suppress radioactive backgrounds and to confirm 𝛽𝛽-decay events. This technique, known as Ba-tagging, comprises extracting and identifying the 𝛽𝛽-decay daughter 136 Ba ion. One tagging approach being pursued involves extracting a small volume of LXe in the vicinity of a potential 𝛽𝛽-decay using a capillary tube and facilitating a liquid-to-gas phase transition by heating the capillary exit. The Ba ion is then separated from the accompanying Xe gas using a radio-frequency (RF) carpet and RF funnel, conclusively identifying the ion as 136 Ba via laser-fluorescence spectroscopy and mass spectrometry. Simultaneously, an accelerator-driven Ba ion source is being developed to validate and optimize this technique. The motivation for the project, the development of the different aspects, along with the current status and results, are discussed here.

a-tagging↗
DOE OSTI2025

Continuum laser absorption spectroscopy of C 2 (a 3 Π u ) in a sublimating cloud of carbon black

A direct optical absorption diagnostic has been developed for rotationally resolved measurements of diatomic carbon (a 3 Π u →d 3 Π g (0,0) and (1,1)) at a repetition rate of 525 kHz and resolution of 7.3 pm over the range of 511.1–514.1 nm. The diagnostic utilizes a high-power pulsed continuum laser light source dispersed in a spectrograph and imaged by a high-speed camera. Measurements have been performed that capture the temporal evolution of C 2 number density and temperature of a cloud of carbon black sublimating in shock heated gas at high temperature and pressure (T = 5500 K, P = 3.7 atm). A simultaneous light absorption measurement of the condensed phase enables comparisons of the gaseous C 2 number density to the condensed phase mass. The continuum laser absorption diagnostic is applied to C 2 in this work but shows promise in being a simple “drop-in” system for absorption spectroscopy in the visible range at rapid repetition rates and high dispersion, filling an important gap for laser diagnostic systems.

Willhardt, Colton Dean [Univ. of Illinois at Urban↗
DOE OSTI2025

Chloride-Based Volatility for Waste Reduction and/or Reuse of Metallic-, Oxide- and Salt-Based Reactor Fuels

The objective of the chloride based volatility project (CBV) was to demonstrate the ability to separate uranium from used fuel to enable process improvements resulting in 10x reduction of waste volume, while maintaining safeguards standards and global backend costs at $\$$1/MW-hr. Current industrial practices perform separations of used fuel using solvent media in the form of aqueous and molten salt processes, resulting in contaminated process waste. The CBV approach utilized solid state chemistry with no solvent media and was successful in chlorinating uranium and fission product oxides that sublimed into the gas phase and were collected in targeted condensation zones based on temperature gradients of chlorinated products. Recovery of better than 95% of initial uranium in the form of UCl4 was demonstrated when simulated used nuclear fuel was used. Laser induced breakdown spectroscopy, LIBS, and ultraviolet-visible spectroscopy, UV-Vis, were combined into a high temperature flow cell design and utilized as process monitoring techniques to observed chlorinated products leave the reaction vessel in real time.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Generative Physics-Informed Neural Network Solving Multi-Scale and Multi-Phase Plasma Chemical Flow Field

Low-temperature plasmas (LTPs) are non-equilibrium systems with near-room-temperature gas and highly energetic electrons. This makes them ideal for delicate applications in biomedicine and semiconductor manufacturing, enabling processes like wound healing, sterilization, etching, and plasma-enhanced chemical vapor deposition without thermal damage. However, LTPs involve complex chemistries, with hundreds of species and thousands of reactions, complicating their diagnosis, prediction, and control. Conventional diagnostics, such as Fourier-transform infrared spectroscopy (FTIR), laser-induced fluorescence (LIF), and optical emission spectroscopy (OES), offer limited species detection, while mass spectrometry (MS) struggles with low-sensitivity species. Additionally, LTP simulations face multi-scale challenges, as macroscopic fluid dynamics and microscopic particle collisions operate on vastly different timescales. To address these issues, we developed an artificial intelligence (AI) based diagnostic system: a generative physics-informed neural network (PINN-Gen) that can predict spatially resolved species concentrations and temperatures in LTPs by integrating experimental data from planar LIF with microscopic plasma chemical kinetics and macroscopic fluid mechanics, including plasma-liquid interactions at the interface between two phases. PINN-Gen solves no equations but checks the errors of physical laws by substituting the output from neural network, and the comparison with the experimental results. Thus, it naturally avoids the multi-scale difficulty of numerical simulations and predicts the results of conventionally unsolvable multi-scale and multi-phase problems. The real-time prediction will be robust due to the physical information used in the training of such a neural network, and only very limited input of condition required due to its generative feature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

2025 ASMS Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS

Title (20 words): Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS Introduction (120 words): One of the challenges facing wide-spread adoption of nuclear power is the development of efficient separation processes for used nuclear fuel. The molecules in separation processes are subjected to an extreme environment due to the high radiation fields from the used fuel and highly acidic media used for fuel dissolution, which results in significant molecular degradation, leading to reduced process efficiency. These degradation products must be identified and studied so mitigation strategies can be developed to maintain process efficiency. However, complex systems can have many degradation products, complicating identification. Untargeted analysis tools could be used to understand radiation chemistry in complex systems. However, this would necessitate improved understanding of the gas-phase fragmentation mechanisms of fuel cycle molecules like tetraoctyldiglycolamide (TODGA). Methods (120 words): The gas-phase fragmentation of protonated TODGA was investigated using collision-induced dissociation (CID), resonance ejection, and infrared ion spectroscopy (IRIS). CID and resonance ejection experiments were conducted using a Bruker Daltonics (Bremen, Gemany) SolariX XR fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. IRIS spectra of protonated TODGA and its two CID fragmentation products were measured using a modified Bruker amaZon Speed ETD 3D quadrupole ion trap mass spectrometer coupled to the Free Electron Lasers for Infrared eXperiments (FELIX) free electron laser. Measured spectra were compared with density functional theory (DFT) calculations using the Gaussian 16, Revision C.02 software package with the ?B97X-D functional and def2-TZVPP basis sets. Candidate structures were generated using the CREST 3.0 conformational sampling software tool. Preliminary Data (300 words): Collision-induced dissociation of protonated TODGA ([C36H73N2O3]+, m/z=581.562) results two fragment ions, one at m/z=340.285 assigned as [C20H38NO3]+ and the other at m/z=312.290, assigned as [C19H38NO2]+. Based on the assigned formula and the structure of protonated TODGA, the fragment at m/z=340.285 is likely formed from elimination of neutral dioctylamine. Comparison of the IRIS spectrum of m/z=340.285 with DFT predictions suggests it contains a ring structure, and is assigned as N-octyl-N-(6-oxo-1,4-dioxan-2-ylidene)octan-1-aminium. Based on this structure and the structure of protonated TODGA, we hypothesize this fragment formed from elimination of neutral dioctylamine followed by a ring closure mechanism. Comparison of the IRIS spectrum of the fragment at m/z=312.290 with DFT predictions also indicated the presence of a ring structure, assigned as N-(1,3-dioxolan-4-ylidene)-N-octyloctan-1-aminium. This product could be formed from elimination of carbon monoxide from the ring of m/z=340.285 as a sequential fragmentation or formed directly from protonated TODGA via elimination of neutral N,N-dioctylformamide followed by a ring closure. Resonance ejection experiments where m/z=340 was continuously ejected from the IRC cell showed no decrease in intensity of m/z=312.290 across several collision energies, suggesting that the later, direct formation mechanism, dominates. The location of the ionizing proton in protonated TODGA is important for modeling the fragmentation mechanisms. DFT calculations suggested that the position of bands involving the coupled vibrations of the amide C—N and C=O bonds in TODGA are the most sensitive to proton location. Evaluation of the IRIS spectrum of protonated TODGA suggests that the ionizing proton is located between the two amid oxygens. This protonation location was calculated to lie approximately 30 kJ/mol lower in energy than the next lowest energy location, with the proton located solely on one of the amide oxygens. Novel aspect (20 words): Infrared ion spectroscopy combined with resonance ejection experiments and density functional theory to probe the collision-induced dissociation mechanism of tetraoctyldiglycolamide.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Chemistry effects on ODS steel consolidated via laser powder bed fusion from GARS powder

Oxide Dispersion Strengthened (ODS) steels are promising candidate alloys for structural and cladding applications in extreme environments. They contain a high density of nanoscale oxides for high temperature mechanical strength and radiation resistance. In this work, gas atomization reaction synthesis (GARS) was used to produce powders that were used for additive manufacturing (AM) Laser Powder Bed Fusion consolidation of ODS steels, in order to skip the traditional mechanical alloying of blended yttria and alloy powders. Powder containing iron, chromium, and tungsten with varying amounts of yttrium, titanium, oxygen and zirconium were used to produce ODS steel samples. AM consolidated specimens and powder samples were characterized with transmission electron microscopy. TEM imaging, diffraction patterns, and energy dispersive X-ray spectroscopy (EDS) was used to identify phases present before and after consolidation across chemistries. The effect of the controlled oxygen input (from GARS) and the oxide-forming additions (Y, Ti, Zr) on precipitate size distribution and composition is substantiated and discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multi-modality deep learning for pulse prediction in homogeneous nonlinear systems via parametric conversion

In this Letter, we introduce FusionNet, a multi-modality deep learning framework designed to predict and analyze output pulses in high-power rare-earth-doped laser systems driving parametric conversion in homogeneous guided nonlinear media. FusionNet integrates temporal, spectral, and physical experimental conditions to model ultrafast nonlinear phenomena, including parametric nonlinear frequency conversion, self-phase modulation, and cross-phase modulation in homogeneous guided systems such as gas-filled hollow-core fibers. These systems bridge physical models with experimental data, advancing our understanding of light-guiding principles and nonlinear interactions while expediting the design and optimization of on-demand high-power, high-brightness systems. Our results demonstrate a 73% reduction in prediction error and an 83% improvement in computational efficiency compared to conventional neural networks. This work establishes a new paradigm for accelerating parametric simulations and optimizing experimental designs in high-power laser systems, with further implications for high-precision spectroscopy, quantum information science, and distributed entangled interconnects.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Impact of target-derived and ambient oxygen on gas-phase oxidation in laser ablation plumes

Gas-phase oxidation in a laser-produced plasma is significantly influenced by the availability of oxygen in and around the plume. In this study, we investigate the role of target-derived and ambient oxygen on AlO formation in plasmas generated from aluminum (Al) and Al 2 O 3 targets in air and argon, respectively. Our results highlight that gas-phase oxidation occurs early during the evolution of Al 2 O 3 plasmas in argon, in contrast to Al plasmas in air, where the initial exclusion of oxygen from the plume delays the chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗