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This final report presents the progress made for the DOE-SC0020623 for the period of performance between January 1 2020 and September 30 2024. The research project is entitled "Kinetic effects of self-organization in low-temperature magnetized plasmas", in which kinetic theory and simulations are used to under stand self-organization patterns.
A central repository of thermophysical and thermochemical properties of molten salt compositions of relevance to molten salt reactors (MSRs) is vital in supporting the broad community of MSR developers, who are at various stages of developing and deploying their reactor designs. In general, these MSR designs differ significantly from developer to developer (e.g., with respect to the hardness of the neutron spectra, level of fissile loading, target multicomponent temperatures and power levels, and moderating capabilities). Therefore, the fuel and coolant salts being considered vary greatly: they may be chlorides or fluorides, they utilize different actinides at different ratios, and the cations in the melt are selected based on perceived advantages and disadvantages. Considering the general need for thermal properties, and the vastness of the array of potential candidate salt mixtures, the Molten Salt Thermal Properties Database (MSTDB) was initiated in 2018 with the goal of providing thermophysical and thermochemical characterization of key molten salt compounds and mixtures across their temperature and compositional domains. The MSTDB is thus divided into the thermophysical arm (MSTDB-TP) and the thermochemical arm (MSTDB-TC). The MSTDB is an effort funded by the Department of Energy, Office of Nuclear Energy (DOE-NE) Nuclear Energy Advanced Modeling and Simulation (NEAMS) program, and the MSR Campaign. This report provides an overview of the MSTDB-TP v4.0 in terms of the data contained within, the state of the tools used to access the data, the availability of predictive models that leverage the raw data in the database, the preliminary status of developmental efforts that are currently underway, and an account of future goals for MSTDB-TP. The primary goal for the update from MSTDB-TP v.3.1 to v4.0 was the incorporation of surface tension data into the database; this property is important for thermal hydraulics modeling and species transport in other tools that have been developed under the NEAMS program. A breakdown of the surface tension data that have been added into MSTDB-TP v4.0 is provided herein, and the manner in which the quality of the data has been assessed is also documented. For MSTDB-TP v4.0, newly published thermophysical property data—primarily from collaborative experimental efforts under the MSR Campaign—have been incorporated into the database, and the resulting expansion is documented here. Because of the size to which MSTDB-TP has grown, the raw data format has now been recast into JavaScript Object Notation (JSON) format for easier connection with the MSTDB-TP application programming interface (API). Saline; the pre-existing comma-separated value (CSV) format has been deprecated but is still maintained, accessible, and up to date. As a final effort in packaging the MSTDB-TP v4.0 update, the graphical user interface (GUI) for MSTDB has been updated to allow full accessibility to the density and viscosity predictive models, which are based on Redlich-Kister expansions of MSTDB-TP raw data. Some other major aspects of this report, in terms of preliminary and future work, include: (1) documentation of the formalism and preliminary testing of a kinetic theory model that may act as a predictive model for thermal conductivity; (2) documentation of the candidate predictive models that may be considered in the future for surface tension, making use of the surface tension data now in MSTDB-TP v4.0; (3) a preliminary account of a data collection process that will enable the filling of additional gaps within MSTDB-TP, namely with data which have been collected computationally (e.g., through ab initio molecular dynamics).
Abstract In magnetic reconnection, the ion bulk outflow speed and ion heating have been shown to be set by the available reconnecting magnetic energy, i.e., the energy stored in the reconnecting magnetic field ( B r ). However, recent simulations, observations, and theoretical works have shown that the released magnetic energy is inhibited by upstream ion plasma beta β i —the relative ion thermal pressure normalized to magnetic pressure based on the reconnecting field—for antiparallel magnetic field configurations. Using kinetic theory and hybrid particle-in-cell simulations, we investigate the effects of β i on guide field reconnection. While previous works have suggested that guide field reconnection is uninfluenced by β i , we demonstrate that the reconnection process is modified and the outflow is reduced for sufficiently large β i > ( B r 2 + B g 2 ) / B r 2 . We develop a theoretical framework that shows that this reduction is consistent with an enhanced exhaust pressure gradient, which reduces the outflow speed as v out ∝ 1 / β i . These results apply to systems in which guide field reconnection is embedded in hot plasmas, such as reconnection at the boundary of eddies in fully developed turbulence like the solar wind or the magnetosheath as well as downstream of shocks such as the heliosheath or the mergers of galaxy clusters.
Abstract Universal acceleration a 0 emerges in various empirical laws, yet its fundamental nature remains unclear. Using Illustris and Virgo N -body simulations, we focus on the velocity and acceleration fluctuations in collisionless dark matter involving long-range gravity. For comparison, in the kinetic theory of gases, molecules undergo random elastic collisions involving short-range interactions, where only velocity fluctuations are relevant. Hierarchical structure formation proceeds through the merging of smaller halos to form larger halos, which facilitates a continuous energy cascade from small to large halos at a constant rate ε u ≈ −10 −7 m 2 s −3 . Velocity fluctuations involve a critical velocity u c ∝ (1 + z ) −3/4 . Acceleration fluctuations involve a critical acceleration a c ∝ (1 + z ) 3/4 . Two critical quantities are related by the rate of energy cascade ε u ≈ − a c u c /[2(3 π ) 2 ], where factor 3 π is from the angle of incidence during merging. With critical velocity u c on the order of 300 km s −1 at z = 0, the critical acceleration is determined to be a c 0 ≡ a c ( z = 0) ≈ 10 −10 m s −2 , suggesting a c might explain the universal acceleration a 0 ≈ 10 −10 m s −2 in the empirical Tully–Fisher relation or modified Newtonian dynamics. The redshift evolution a c ∝ (1 + z ) 3/4 is in good agreement with Magneticum and EAGLE simulations and in reasonable agreement with limited observations. This suggests a larger a 0 at a higher redshift such that galaxies of fixed mass rotate faster at a higher redshift. Note that for dark energy (DE) density ρ DE 0 ≈ a c 0 2 / G = 1 0 − 10 J m −3 , we postulate an entropic origin of the DE from acceleration fluctuations of dark matter, analogous to the gas pressure from velocity fluctuations. This leads to a dynamical DE coupled to the structure evolution involving a relatively constant DE density followed by a slow weakening phase, suggesting possible deviations from the standard ΛCDM paradigm.
Catalytic hydrodechlorination is a promising strategy for treating industrial 1,2-dichloroethane wastes, for which Pt and Pt-based alloy catalysts are widely used. Here, we performed a detailed mechanistic study for 1,2-dichloroethane hydrodechlorination on Pt using a synergistic approach combining density functional theory (DFT) calculations, reaction kinetics experiments, and microkinetic modeling. Using planewave DFT calculations, we evaluated the reaction energy and activation energy barrier of each elementary step involved in the reaction network on Pt(111). The calculated energetics were then incorporated into a comprehensive mean-field microkinetic model accounting for a total of 65 elementary steps. The model-predicted reaction rates were compared with the results from our reaction kinetics experiments on SiO2-supported Pt catalysts. Our results indicated that the hydrodechlorination of 1,2-dichloroethane on Pt(111) starts with a H-removal step; then, it proceeds through a sequence of alternating dechlorination and dehydrogenation steps until vinylidene (CH 2 C*) is formed; finally, CH 2 C* is hydrogenated to the final product, ethane, sequentially via vinyl (CH 2 CH*), ethylene, and ethyl (CH 3 CH 2 *) intermediates. After model parameter adjustments, we achieved good agreement between our theoretical model and experimental results; the adjustments to the calculated parameters are consistent with the typically anticipated coverage effects. Furthermore, our study offers valuable mechanistic insights, which are useful for improving catalysts for this chemistry.
The ubiquitous two-step Michaelis–Menten and Temkin–Boudart reaction mechanisms are extended to include the influence of the catalyst electronic subsystem in a 5-step mechanism. The resulting kinetic equation provides an alternative explanation for the well-known volcano-shaped dependence found in catalysis. The equilibrium constants of fast electronic steps are highlighted for their influence on adsorption and desorption through the relative concentration of charged versus neutral intermediates. This generalized concept can be widely applied to determine the optimal catalyst, based on the Fermi level of the material, for reactions proceeding via this universal reaction.
Over the past 20 to 25 years theoretical chemistry (particularly theoretical chemical kinetics) has played an increasingly important role in developing chemical kinetics models for combustion. Theoretical methods of obtaining rate parameters are now competitive in accuracy with experiment, particularly for small molecules. Moreover, theoretical methods can deal with conditions that experiments frequently cannot. In addition to increased accuracy, theory has rejuvenated methods and discovered phenomena that were completely unappreciated, or at least underappreciated, in the 20th century. Our primary interest here is in molecular-level issues, i.e. in calculating rate and transport parameters. However, dealing with kinetics models that involve thousands of reactions and hundreds of species is important for practical applications and is relatively new to the 21st century. Theory, in a general sense, and theoretical methods development have a role to play here too. We discuss in this review all these topics in some detail with an emphasis on issues and methods that have emerged in the last 20 years or so. Even so, our review is selective, rather than comprehensive, out of necessity.
The increasing demand for high-performance materials in advanced technologies highlights the importance of achieving a fundamental understanding and potential control of silicon carbide (SiC) deposition processes. However, existing models often lack sufficient theoretical detail, relying heavily on empirical data and offering limited predictive capability. In particular, the complex surface chemistry governing SiC growth remains poorly understood. This study addresses these challenges by employing density functional theory (DFT) to investigate key heterogeneous reactions involving hydrocarbon intermediates on SiC surfaces, including dehydrogenation, hydrogenation, and carbon deposition. Transition state searches were conducted to identify reaction pathways and energy barriers. While first-principles calculations offer high accuracy, they are computationally intensive. To extend the utility of these first-principles results, vibrational analyses were performed using phonon-based statistical thermochemistry to compute temperature-dependent reaction rates which were used to develop Arrhenius-type surrogate kinetic models. Furthermore, the resulting framework provides a more rigorous, physically grounded basis for integrating atomistic insights into continuum-scale modeling, ultimately enabling improved prediction and optimization of SiC film growth in high-performance material systems.
X-ray spectroscopy has long been a powerful diagnostic tool for hot, dilute plasmas, providing insights into plasma conditions by measuring line shifts and broadenings of atomic transitions. The technique critically depends on the accuracy of atomic physics models used to interpret spectroscopic measurements for inferring plasma properties such as free-electron density and temperature. Over the past decades, the atomic and plasma physics communities have developed robust atomic physics models to account for various processes in hot, dilute classical plasmas. While these models have been successful in that regime, their applicability becomes uncertain when interpreting x-ray spectroscopy experiments of above-solid-density plasmas. Given that finite-temperature density-functional theory (DFT) offers a more accurate description of dense plasma environments, we present the development of a DFT-based multi-band kinetic model, VERITAS, designed to improve the interpretation of x-ray spectroscopic measurements in high-density plasmas produced by laser-driven spherical implosions. This work details the VERITAS model and its application to both time-integrated and time-resolved x-ray spectra from implosion experiments on OMEGA. The advantages and limitations of the VERITAS model will also be discussed, along with potential directions for advancing x-ray spectroscopy of dense and superdense plasmas.
Hydrogen transfer is a critical component of many chemical and biological processes. The ratio of rate constants for hydrogen and deuterium transfer defines the H/D kinetic isotope effect (KIE), which is a powerful tool for elucidating hydrogen transfer mechanisms. Interpretation of experimental H/D KIEs relies on accurate and affordable computational methods. However, due to their light mass, hydrogen and deuterium can undergo tunneling, which is challenging to describe in multidimensional molecular systems. Herein, we introduce the nuclear–electronic orbital general rate theory (NEO-GRT), which enables the efficient prediction of H/D KIEs based on full-dimensional molecular quantum chemistry calculations. The NEO-GRT approach describes the hydrogen transfer rate constant with a general expression that spans the vibrationally adiabatic and nonadiabatic hydrogen tunneling regimes. The input quantities are computed using NEO density functional theory, which treats the transferring hydrogen or deuterium nucleus quantum mechanically on the same level as the electrons. We investigate two intramolecular proton transfer reactions in organic molecules at temperatures down to 50 K to evaluate the performance of NEO-GRT by comparison to transition state theory and ring-polymer instanton theory. The KIEs computed with NEO-GRT agree with those calculated using ring-polymer instanton theory for the full-dimensional molecular systems at the same level of electronic structure theory. This agreement indicates that NEO-GRT captures the deep hydrogen tunneling effects, in contrast to transition state theory, which neglects such effects. Given its relatively low computational cost, NEO-GRT is a promising approach for predicting H/D KIEs in large organic and organometallic systems.
The illumination of catalytic surfaces with a continuous or pulsed stream of photons dynamically modulates surface chemistry for faster rates, non-equilibrium conversion, or product selectivity control. To establish fundamental principles of dynamic photon-modulated catalysis, the photocatalytic conversion of a generic surface reaction was simulated using the kinetic Monte Carlo method to understand the kinetic implications of an independent stream of photons that promotes surface product desorption. The time-averaged photocatalytic rate at differential conditions for varying photon flux and temperatures indicated three kinetic regimes described by product thermal desorption control, surface reaction control, and an intermediate kinetic regime with a zero slope Arrhenius plot, consistent with a degree of rate control dominated by the photon arrival frequency (i.e., per-site photon flux). Here, the maximum photocatalytic rate occurred orders of magnitude above the Sabatier limit at the resonance frequency, identified as the photon arrival frequency matching the surface reaction rate constant.
Multi-step surface chemistry promoted with one or two wavelengths of light exhibited distinct kinetic signatures indicative of the light-adsorbate interactions and the number of photon-sensitive elementary steps. In this work, kinetic Monte Carlo simulations identified the kinetic response of general surface mechanisms to variation in the per-site photon flux of one or two wavelengths of incident light. Photocatalytic rates were described via a non-dimensional photon flux, identifying multiple kinetic regimes with unique degrees of rate control. Under photon-controlled kinetic conditions, maximum quantum yield and turnover frequency were obtained under constant illumination, while pulsing of one or more light sources was shown to exhibit slower rates and less efficient photocatalytic promotion due to the inherent dynamic nature of light, which comprises a stream of photons. Simulations provided distinct kinetic signatures in catalytic rates and Arrhenius kinetics for specific light-surface-adsorbate interactions corresponding to photocatalytic promotion of specific steps in surface chemistry.
The complexity of programmable catalysts that change in the physical or electronic state on the time scale of a catalytic turnover results in uncertainty in the kinetic outcome of common measurements with dynamic catalyst experiments. To provide an interpretation of utility to experimentalists, a general programmable catalytic reaction exhibiting high turnover efficiency was simulated to understand the kinetic behavior of catalysts with varying frequency, binding energy, oscillation amplitude, and minimum oscillation binding energy at different temperatures and reactant gas pressures. The time-averaged catalytic rate for varying temperature in the form of an Arrhenius plot exhibited three distinct kinetic regimes, with the intermediate temperatures or applied frequencies exhibiting zero slope, indicative of barrier-free kinetic control. Transitions in experimentally measurable kinetic regimes with both temperature and applied catalyst oscillation frequency were associated with transitions in the sensitivity of reaction rate constants and degrees of rate control. Furthermore, these distinct kinetic macroscopic features specific to programmable catalysts were identified for observation in experimental dynamic kinetic measurements.
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The kinetic energy-dependent reactions of the atomic actinide uranium cation (U + ) with H 2 , D 2 , and HD were examined by guided ion beam tandem mass spectrometry. An average 0 K bond dissociation energy of D 0 (U + – H) = 2.48 ± 0.06 eV is obtained by analysis of the endothermic product ion cross sections. Quantum chemistry calculations were performed for comparison with experimental thermochemistry, including high-level CASSCF–CASPT2–RASSI calculations of the spin–orbit corrections. CCSD(T) and the CASSCF levels show excellent agreement with experiment, whereas B3LYP and PBE0 slightly overestimate and the M06 approach badly underestimates the bond energy for UH + . Theory was also used to investigate the electronic structures of the reaction intermediates and potential energy surfaces. The experimental product branching ratio for the reaction of U + with HD indicates that these reactions occur primarily via a direct reaction mechanism, despite the presence of a deep-well for UH 2 + formation according to theory. The reactivity and hydride bond energy for U + are compared with those for transition metal, lanthanide, and actinide cations, and periodic trends are discussed. Furthermore, these comparisons suggest that the 5f electrons on uranium are largely core and uninvolved in the reactive chemistry.
The general quasilinear Fokker–Planck kinetic equation for the gyrophase-averaged plasma particle distribution functions in magnetized plasmas is derived, making no restrictions on the energy of the particles and on the frequency of the electromagnetic fluctuations and avoiding the often made Coulomb approximation of the electromagnetic interactions. Here, the inclusion of discrete particle effects breaks the dichotomy of nonlinear kinetic plasma theory divided into the test particle and the test fluctuation approximation because it provides expression of both the non-collective and collective electromagnetic fluctuation spectra in terms of the plasma particle distribution functions. Within the validity of the quasilinear approach, the resulting full quasilinear transport equation can be regarded as a determining nonlinear equation for the time evolution of the plasma particle distribution functions.
Blob-filaments (or simply “blobs”) are coherent structures formed by turbulence and sustained by nonlinear processes in the edge and scrape-off layer (SOL) of tokamaks and other magnetically confined plasmas. The dynamics of these blob-filaments, in particular, their radial motion, can influence the scrape-off layer width and plasma interactions with both the divertor target and with the main chamber walls. Motivated by recent results from the XGC1 gyrokinetic simulation code reported on elsewhere [J. Cheng et al., Nucl. Fusion 63, 086015 (2023)], a theory of rapidly spinning blob-filaments has been developed for this work. The theory treats blob-filaments in the closed flux surface region or the region that is disconnected from sheaths in the SOL. It extends previous work by treating blob spin, arising from partially or fully adiabatic electrons, as the leading-order effect and retaining inertial (ion charge polarization) physics in next order. Spin helps to maintain blob coherency and affects the blob's propagation speed. Dipole charge polarization, treated perturbatively, gives rise to blob-filaments with relatively slow radial velocity, comparable to that observed in the simulations. The theory also treats the interaction of rapidly spinning blob-filaments with a zonal flow layer. It is shown analytically that the flow layer can act like a transport barrier for these structures. Finally, parallel electron kinetic effects are incorporated into the theory. Various asymptotic parameter regimes are discussed, and asymptotic expressions for the radial and poloidal motion of the blob-filaments are obtained.
Accurate knowledge of the electronic transport properties of warm dense matter is one of the main concerns of research in high-energy-density physics. Three modern approaches with vastly different levels of fidelity are reviewed and compared: the Kubo–Greenwood (KG) approach based on density-functional-theory molecular dynamics simulations (QMD), quantum kinetic theory based on average-atom models, and time-dependent density functional theory. Throughout, emphasis is placed on the connection between static properties of the electrons (e.g., density of states) and transport properties. Overall, it is found that whenever the conduction electrons can be modeled as being nearly free, fair to excellent agreement is found between QMD and kinetic theory approaches. Such a circumstance is required for modeling warm dense matter as a plasma of ions and free electrons, which is assumed in most kinetic theory approaches. The sensitivity of transport properties to the electronic structure is further highlighted by comparing different exchange–correlation approximations in QMD and KG calculations. It is found that the inclusion of exact exchange via thermal hybrid functionals can make a pronounced impact on electrical and thermal conduction in warm dense matter. We also investigate dynamic screening physics via kinetic theory and time-dependent density functional theory calculations of the mean free path of an electron in a hot dense plasma. In sum, we identify three axes along which to make progress in predicting electron transport in warm dense matter.