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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

In 1922, Lindemann proposed the now-well-known mechanism for pressure-dependent rate constants for unimolecular reactions: reactant molecules with sufficiently high energies dissociate more quickly than collisions can reestablish the Boltzmann distribution of the internal energies of the molecule during its dissociation at low pressures – yielding pressure-dependent rate constants for unimolecular reactions due to the preferential depletion of the high energy states capable of dissociation. In the last century, incredible progress has been made in achieving a far greater understanding of and quantitative predictions for unimolecular and association reactions. In the modern era, pressure-dependent phenomenological rate constants are now nearly universally used to describe the rates of unimolecular and associative reactions in phenomenological kinetic modeling. However, there is a second, more indirect, implication of Lindemann’s mechanism that relates to how these dissociation-induced non-equilibrium distributions impact bimolecular reactions, including non-associative bimolecular reactions – which are generally not considered to have pressure-dependent rate constants. Yet, as we show herein, the same high energy states depleted due to dissociation would otherwise react most rapidly in high-activation-energy bimolecular reactions – yielding a mechanism for pressure-dependent rate constants for bimolecular reactions (including non-associative reactions). Here, we present results from a case study for CH 2 O dissociation, isomerization, and bimolecular reaction with O2 to explore this question. Results from our master equation calculations indicate that the effect of dissociation-induced non-equilibrium distributions on bimolecular reactions can be substantial – even when chemical timescales are well separated from internal energy relaxational timescales (i.e. when the traditional rate constant description would be thought to apply). This effect is found to be more pronounced – and more complex – for bimolecular reactions involving molecular entities whose chemical timescales are merged with the internal energy relaxational timescales. Lastly, we present some ideas for discussion regarding what should be considered as “chemical species” in phenomenological kinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Quantization effects in semiconductor nanostructures and singlet fission in molecular chromophores for photovoltaics and solar fuels

Hot carriers in semiconductors are electrons and/or holes that have energies greater than carriers that reside at the top and bottom of the conduction and valence bands, respectively; the latter carriers are in equilibrium with the lattice and have a temperature equal to the lattice (ambient) temperature. Hot carriers are created in semiconductors upon the absorption of photons with energies greater than the bandgap. The excess energy above the bandgap energy is in the form of kinetic energy. The hot carriers can cool to the lattice temperature via electron–phonon scattering and establish separate Boltzmann distributions for electrons and holes at the band edges. Thus, upon cooling, the excess kinetic energy of the hot carriers is transformed into heat and is unavailable to be converted into electrical or chemical free energy in a solar photon-converting cell. This hot-carrier cooling process significantly limits the maximum possible power conversion efficiency (PCE) of the free energy of solar photons into electrical free energy or chemical free energy in chemical bonds of fuels. However, if hot-carrier cooling can be slowed such that the hot carriers can be extracted before cooling to create higher photovoltages, or utilized to create additional electron-hole pairs through carrier multiplication, then beneficial use can be made of the excess energy of hot carriers and the maximum thermodynamic PCE can be dramatically increased. Quantization effects in semiconductor nanostructures, unique properties of some bulk semiconductors, and exciton multiplication in both semiconductors and molecular chromophores that undergo singlet fission have shown a path forward for potential dramatic increases in the PCEs of solar photons into electricity and solar fuels. The status, history, and future promise of the science and technology of these future approaches for different types of photovoltaic cells and cells for solar fuels will be discussed.

14 SOLAR ENERGY↗
DOE OSTI2021

Bringing discrete-time Langevin splitting methods into agreement with thermodynamics

In light of the recently published complete set of statistically correct Grønbech–Jensen (GJ) methods for discrete-time thermodynamics, we revise a differential operator splitting method for the Langevin equation in order to comply with the basic GJ thermodynamic sampling features, namely, the Boltzmann distribution and Einstein diffusion, in linear systems. This revision, which is based on the introduction of time scaling along with flexibility of a discrete-time velocity attenuation parameter, provides a direct link between the ABO splitting formalism and the GJ methods. This link brings about the conclusion that any GJ method has at least weak second order accuracy in the applied time step. It further helps identify a novel half-step velocity, which simultaneously produces both correct kinetic statistics and correct transport measures for any of the statistically sound GJ methods. Explicit algorithmic expressions are given for the integration of the new half-step velocity into the GJ set of methods. Finally, numerical simulations, including quantum-based molecular dynamics (QMD) using the QMD suite Los Alamos Transferable Tight-Binding for Energetics, highlight the discussed properties of the algorithms as well as exhibit the direct application of robust, time-step-independent stochastic integrators to QMD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Comparison of excitation temperature of a laser-produced plasma by combining emission and absorption spectroscopy

Measurement of the temporal evolution of laser-produced plasma temperature is very important for many of its applications, and several plasma diagnostic tools are routinely used by researchers. However, it is very challenging to measure the properties of the plasma at the early and late times of its evolution using a single diagnostic tool. In this study, we combined emission and laser absorption spectroscopy to compare the excitation temperatures of a laser-produced uranium plasma system. Several U I transitions in the near-infrared spectral range (775–800 nm) were considered, and the Boltzmann plot method was used to measure the excitation temperatures using both emission and absorption spectroscopy. Emission spectroscopy provided early-time temperature measurements of the plasma up to times 2–20 µs, while absorption spectroscopy provided temperature measurements at late times of plasma evolution (for times 5–80 µs). The emission and absorbance of U I transitions were found to follow the Boltzmann distribution, indicating the plasma is likely in the state of local thermodynamic equilibrium even at late times of its lifetime. The emission and absorption-based time-resolved excitation temperatures demonstrated good agreement at earlier times (≤15 µs) in the overlapped temporal region, while a deviation in the measured values was seen at times (≥15 µs), and potential reasons for such a disagreement are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Review and meta-analysis of electron temperatures from high-intensity laser–solid interactions

The accelerated electron spectrum from high-intensity laser–solid interaction is often conveniently described using a Boltzmann distribution, whose temperature is known within the field as the hot-electron temperature. The importance of the electron temperature is highlighted by the sheer number of experimental and simulation studies on the subject over the past three decades. Recently, multi-kJ, multi-ps pulses have yielded electron spectra with temperatures far beyond the expected ponderomotive result. Expressions that predict the electron temperature considering laser parameters beyond intensity and wavelength have been developed, albeit using small datasets. In this review, we present what is, to the best of our knowledge, the largest dataset of electron temperatures gathered from experimental measurements and particle-in-cell simulations. This dataset allows us to compare existing analytical and empirical hot-electron temperature scaling models over a wide parameter range. We also develop new scaling models that incorporate the laser pulse duration of the laser and the plasma scale length. Three models that include pulse-duration and scale length dependence are especially successful at predicting both simulated and experimental data. The dataset will soon be made publicly available to encourage further investigation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Dynamical instability of collapsed dark matter halos

A self-interacting dark matter halo can experience gravothermal collapse, resulting in a central core with an ultrahigh density. It can further contract and collapse into a black hole, a mechanism proposed to explain the origin of supermassive black holes. We study dynamical instability of the core in general relativity. Here we use a truncated Maxwell-Boltzmann distribution to model the dark matter distribution and solve the Tolman-Oppenheimer-Volkoff equation. For given model parameters, we obtain a series of equilibrium configurations and examine their dynamical instability based on considerations of total energy, binding energy, fractional binding energy, and adiabatic index. Our numerical results indicate that the core can collapse into a black hole when the fractional binding energy reaches 0.035 with a central gravitational redshift of 0.5. We further show for the instability to occur in the classical regime, the boundary temperature of the core should be at least 10% of the mass of dark matter particles; for a 10 9 M ⊙ seed black hole, the particle mass needs to be larger than a few keV. These results can be used to constrain different collapse models, in particular, those with dissipative dark matter interactions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

High-performance nanodevices based on WGe 2⁢ N 4 monolayer

Two-dimensional (2D) 𝑀⁢𝐴 2 ⁢𝑍 4 -family monolayers (MLs) have emerged as promising semiconductors due to their element tunability and rich electronic and optoelectronic properties. In this work, using first-principles calculations, we investigate the electronic, mechanical, transport, and optoelectronic properties of WGe 2⁢ N 4 ML with a small indirect bandgap. Various nanodevices based on WGe 2 ⁢N 4 ML are studied, including pn-junction diodes, pin-junction field-effect transistors (FETs), and phototransistors. The present results reveal that the WGe 2⁢ N 4 ML exhibits high rigidity, thermal stability, and remarkable light absorption. These nanodevices demonstrate excellent performance: (1) the pn-junction diode shows a high rectification ratio and a near-Shockley-limit ideality factor, (2) the pin-junction FET exhibits significant gate voltage modulation capability with subthreshold swing as low as 71 mV/dec (close to the theoretical limit calculated based on the Boltzmann distribution), and (3) the phototransistor displays strong optoelectronic responses in the visible and ultraviolet regions. Furthermore, these findings establish WGe 2 ⁢N 4 ML as a versatile platform for developing high-performance, multifunctional nanoelectronic and optoelectronic devices, significantly expanding the application potential of 𝑀⁢𝐴 2⁢ 𝑍 4 -family materials.

2-dimensional systems↗
DOE OSTI2022

Fate of multiparticle resonances: From Q-balls to 3 He droplets

We study a system of N nonrelativistic particles which form a near-threshold resonance. Assuming no subset of these particles can form a bound state, the resonance can only decay through an “explosion” into N particles. We find that the decay width of the resonance scales as E Δ –5/2 in the limit when the energy E of the resonance goes to zero, where Δ is the ground-state energy of a system of N particles in a spherical harmonic trap with unit frequency. Here, the formula remains valid when some pairs of final particles have zero-energy s-wave resonance, but the Efimov effect is not present. In the limit of large N, we show that the final particles follow a Maxwell-Boltzmann distribution if they are bosons and a semicirclelike law if they are fermions. We expect our general result to be applicable to various systems that exist in nature. In particular, we argue that metastable 3 He droplets exist with the lifetime varying over many orders of magnitude ranging from a fraction of a nanosecond to values greatly exceeding the age of the Universe.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

High-temperature ion-thermal behavior from average-atom calculations

Atom-in-jellium calculations of the Einstein frequency were used to calculate the mean displacement of an ion over a wide range of compression and temperature. Expressed as a fraction of the Wigner-Seitz radius, the displacement is a measure of the asymptotic freedom of the ion at high temperature, and thus of the change in heat capacity from six to three quadratic degrees of freedom per atom. A functional form for free energy was proposed based on the Maxwell-Boltzmann distribution as a correction to the Debye free energy, with a single free parameter representing the effective density of potential modes to be saturated. Finally, this parameter was investigated using molecular dynamics simulations, and found to be ~0.2 per atom. In this way, the ion-thermal contribution can be calculated for a wide-range equation of state (EOS) without requiring a large number of molecular dynamics simulations. Example calculations were performed for carbon, including the sensitivity of key EOS loci to ionic freedom.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Urca Cooling in Neutron Star Crusts and Oceans: Effects of Nuclear Excitations

We report the excited-state structure of atomic nuclei can modify nuclear processes in stellar environments. In this Letter, we study the influence of nuclear excitations on Urca cooling (repeated back-and-forth β decay and electron capture in a pair of nuclear isotopes) in the crust and ocean of neutron stars. We provide for the first time an expression for Urca process neutrino luminosity which accounts for a thermal Boltzmann distribution of excited states in both members of an Urca pair. We use our new formula with state-of-the-art nuclear structure inputs to compute neutrino luminosities of candidate Urca cooling pairs. Our nuclear inputs consist of the latest experimental data supplemented with calculations using the projected shell model. We show that, in contrast to previous results that only consider the ground states of both nuclei in the pair, our calculated neutrino luminosities for different Urca pairs vary sensitively with the environment temperature and can be radically different from those obtained in the one-transition approximation. We find that nuclear excitations can lead to an enhancement in total Urca neutrino luminosities in the accreted neutron star crust by about 5 times as compared with the previous Urca results, which is expected to cause significant observational effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Simultaneous single-shot rotation–vibration non-equilibrium thermometry using pure rotational fs/ps CARS coherence beating

Here, we report the development of a simple and sensitive two-beam hybrid femtosecond/picosecond pure rotational coherent anti-Stokes Raman scattering (fs/ps CARS) method to simultaneously measure the rotational and vibrational temperatures of diatomic molecules. Rotation–vibration non-equilibrium plays a key role in the chemistry and thermalization in low-temperature plasmas as well as thermal loading of hypersonic vehicles. This approach uses time-domain interferences between ground state and vibrationally excited N 2 molecules to intentionally induce coherence beating that leads to apparent non-Boltzmann distributions in the pure rotational spectra. These distortions enable simultaneous inference of both the rotational and vibrational temperatures. Coherence beating effects were observed in single-shot fs/ps CARS measurements of a 75 Torr N 2 DC glow discharge and were successfully modeled for rotational and vibrational temperature extraction. We show that this method can be more sensitive than a pure rotational fs/ps CARS approach using a spectrally narrow probe pulse. Lastly, we experimentally measured the beat frequencies via Fourier transform of the time-domain response and obtained excellent agreement with the model.

42 ENGINEERING↗
DOE OSTI2024

One-dimensional temperature measurement of supersonic jet flow by resonantly ionized photoemission thermometry of molecular nitrogen

As the field of fluid dynamics progresses, the demand for sophisticated diagnostic methods to accurately assess flow conditions rises. In this work, resonantly ionized photoemission thermometry (RIPT) has been used to directly target and ionize diatomic nitrogen (N 2 ) to measure one-dimensional (1D) temperature profiles in a supersonic jet flow. This technique can be considered non-intrusive as the premise uses resonantly enhanced multiphoton ionization (REMPI) to target molecular nitrogen. This resonance excites N 2 into absorption bands of the P, Q, and R rotational branches of N 2 ( b 1 Π u ). The ideal (3 + 1) REMPI scheme excites from the ground state and ionizes N 2 ( b 1 Π u ← X 1 Σ g + ) where de-excitation results in photoemission from the first negative band of ionized N 2 + ( B 2 Σ u + → X 2 Σ g + ) as nitrogen returns to the ground state. The resulting emission can be observed using an intensified camera, thus permitting inference of the rotational temperature of ground-state molecular nitrogen. A linearly regressive Boltzmann distribution is applied based on previous calibration data for this technique to quantify the temperature along the ionized line. This work applies this technique to a pure N 2 supersonic jet in cross-flow and counter-flow orientations to demonstrate N 2 RIPT’s applications in a supersonic flow. Temperature variations are observed at different locations downstream of the exit in cross-flow, and axisymmetric in counter-flow, to generate profiles characterizing the flow dynamics. Due to the collisional effects resulting from the number density of N 2 at higher pressures, a (3 + 2) REMPI scheme is observed throughout this text.

Clark, Aleksander (ORCID:0009000855600042)↗
DOE OSTI2020

CI-MBPT and Intensity-Based Lifetime Calculations for Th II

Lifetime calculations of Th II J = 1.5 and 2.5 odd states are performed with configuration–interaction many-body perturbation theory (CI-MBPT). For many J = 2.5 states, lifetimes are quite accurate, but two pairs of J = 2.5 odd states and many groups of J = 1.5 states are strongly mixed, making theoretical predictions unreliable. To solve this problem, a method based on intensities is used. To relate experimental intensities to lifetimes, two parameters, one an overall coefficient of proportionality for transition rates and one temperature of the Boltzmann distribution of populations, are introduced and fitted to minimize the deviation between theoretical and intensity-derived lifetimes. For strongly mixed groups of states, the averaged lifetimes obtained from averaged transition rates were used instead of individual lifetimes in the fit. Close agreement is obtained. Then intensity branching ratios are used to extract individual lifetimes for the strongly mixed states. The resulting lifetimes are compared to available directly measured lifetimes and reasonable agreement is found, considering limited accuracy of intensity measurements. The method of intensity-based lifetime calculations with fit to theoretical lifetimes is quite general and can be applied to many complex atoms where strong mixing between multiple states exists.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1972

Excitation of sodium D-line radiation in collisions of sodium atoms with internally excited H2, D2 and N2.

Excitation of D-line radiation in collisions of Na atoms with vibrationally excited N2, H2, and D2 was studied in two modulated crossed-beam experiments. In both experiments, the molecular excitation was provided by heating the molecular beam to temperatures which were assumed to give populations corresponding to the Boltzmann distribution. In the first experiment, a total rate coefficient was measured as a function of molecular beam temperature. The second experiment achieved partial separation of internal vs kinetic energy transfer effects by using a velocity-selected molecular beam. The data from both experiments were used to determine parameters for the dependence of the transfer cross section upon the kinetic energy for a given change in the vibrational quantum number. Results indicate that most of the Na excitation energy comes from internal vibrational energy, with the remainder coming from kinetic energy.

Krause, H. F.↗
NASA NTRS1973

The hydroperoxyl radical in atmospheric chemical dynamics - Reaction with carbon monoxide.

Discussion of laboratory measurements which indicate that the reaction of the thermalized HO(2) radical with CO is exceedingly slow and that this reaction should not, therefore, be of any significance in atmospheric chemistry. The large discrepancy between the new results and data obtained earlier by Westenberg and de Haas (1972) is explained in terms of the reacting hydroperoxyl radical being in a non-Boltzmann distribution in the former study. It appears that the most important reactions of thermalized HO(2) in the atmosphere are those involving the trace gases of NO and sulfur dioxide.

Davis, D. D.↗