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Enabling Nuclear and Solar Thermal Propulsion with the Computational Laboratory: Faster and Cheaper Materials Characterization

Nuclear and solar thermal propulsion offer enhanced efficiencies for in-space travel which may open up the outer Solar System to both crewed and automated craft. However, these advanced propulsion systems require cutting-edge materials which are often not easily tested in the laboratory. Ab initio thermodynamics and other computational methods offer a way to test materials at high pressures and temperatures more quickly, and with reduced cost. Here, several case studies are presented which highlight the utility of modern simulation techniques. First, an extensive thermodynamic study was performed at the ab initio level to elucidate the role of hot hydrogen flow on the erosion of four refractory carbides to examine their appropriateness for use as channel coatings. A detailed analysis of reaction products informs estimates of erosion which are validated in comparison with heritage NERVA data. Specific material suggestions are made for both nuclear and solar designs. Secondly, we examined the mechanical behavior and chemical stability of various components of an idealized nuclear cermet core design using techniques spanning from the atomic to microscale. Next, the mechanical and chemical behavior of tungsten (a potential matrix material) and the stability of uranium mononitride (a potential ceramic fuel element), are characterized in the presence of hydrogen and at elevated temperatures with ab initio thermodynamics. Finally, the mechanical response and failure of tungsten under tensile strain is simulated at the micron scale with a combined finite element and dislocation dynamics approach. The resultant stress-strain data agrees well with experiments and leads to a workflow which can incorporate ab initio thermodynamic data into micron-scale simulations and thus provide real-world relevant estimates of erosion and stress-strain behavior. The power of this framework and our plans to use it in the future will be discussed.

William C Tucker↗

DOE OSTI2023

True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications

The true molecular conformation and the crystal structure of benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene, 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene were determined ab initio by 3D electron diffraction. All three molecules are remarkable polycyclic aromatic hydrocarbons. The molecular conformation of two of these compounds could not be determined via classical spectroscopic methods due to the large size of the molecule and the occurrence of multiple and reciprocally connected aromatic rings. The molecular structure of the third molecule was previously considered provisional. These compounds were isolated as by-products in the synthesis of similar products and were at the same time nanocrystalline and available only in very limited amounts. 3D electron diffraction data, taken from submicrometric single crystals, allowed for direct ab initio structure solution and the unbiased determination of the internal molecular conformation. Detailed synthetic routes and spectroscopic analyses are also discussed. Based on many-body perturbation theory simulations, benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene may be a promising candidate for triplet–triplet annihilation and 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene may be a promising candidate for intermolecular singlet fission in the solid state.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Spectroscopy on the A 1 Π←X 1 Σ + Transition of Buffer-Gas Cooled AlCl

Aluminum monochloride (AlCl) has been proposed as an excellent candidate for laser cooling. Here we present absorption spectroscopy measurements on the A 1 Π←X 1 Σ + transition in AlCl inside a cryogenic helium buffer-gas beam cell. The high resolution absorption data enables a rigorous, quantitative comparison with our high-level ab initio calculations of the electronic and rovibronic energies, providing a comprehensive picture of the AlCl quantum structure. Further, the combination of high resolution spectral data and theory permits the evaluation of spectroscopic constants and associated properties, like equilibrium bond length, with an order of magnitude higher precision. Based on the measured molecular equilibrium constants of the A 1 Π state, we estimate a Franck-Condon factor of the A 1 Π←X 1 Σ + of 99.88%, which confirms that AlCl is amenable to laser cooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

Accurate ab initio quartic force fields for borane and BeH2

The quartic force fields of BH3 and BeH2 have been computed ab initio using an augmented coupled cluster (CCSD(T)) method and basis sets of spdf and spdfg quality. For BH3, the computed spectroscopic constants are in very good agreement with recent experimental data, and definitively confirm misassignments in some older work, in agreement with recent ab initio studies. Using the computed spectroscopic constants, the rovibrational partition function for both molecules has been constructed using a modified direct numerical summation algorithm, and JANAF-style thermochemical tables are presented.

Martin, J. M. L.↗

NASA NTRS2016

Computing Highly Accurate Spectroscopic Line Lists for Characterization of Planetary Atmospheres: CO2 and SO2 Line Lists Needed for Modeling Venus

Over the last decade, it has become apparent that the most effective approach for determining highly accurate rotational and rovibrational line lists for molecules of interest in planetary atmospheres and other astrophysical environments is through a combination of highresolution laboratory experiments coupled with state-of-the art ab initio quantum chemistry methods. The approach involves computing the most accurate potential energy surface (PES) possible using state-of-the art electronic structure methods, followed by computing rotational and rovibrational energy levels using an exact variational method to solve the nuclear Schrödinger equation. Then, reliable experimental data from high-resolution experiments is used to refine the ab initio PES in order to improve the accuracy of the computed energy levels and transition energies. From the refinement step, we have been able to achieve an accuracy of approximately 0.015 cm-1 for rovibrational transition energies, and even better for purely rotational transitions. This combined "experiment / theory" approach allows for determination of essentially a complete line list, with hundreds of millions of transitions, and having the transition energies and intensities be highly accurate. Our group has successfully applied this approach to determine highly accurate line lists for NH3, CO2 and isotopologues, and SO2 and isotopologues. Here I will report our latest results for CO2 and SO2 including all isotopologues. Comparisons to the available data in HITRAN2012 and other available databases will be shown, though we note that our line lists for SO2 are significantly more complete than any other databases. Since it is important to span a large temperature range in order to model the spectral signature of Venus as well as exoplanets, we will demonstrate how the spectra change on going from low temperatures (100 K) to higher temperatures (500 K to 1500 K).

potential energy surface (PES)5405 PLANETARY SCIEN↗

DOE OSTI2022

Revisit the VEC criterion in high entropy alloys (HEAs) with high-throughput ab initio calculations: A case study with Al-Co-Cr-Fe-Ni system

Valence electron concentration (VEC) was treated as a useful parameter to predict the stability of solid solution phases. However, the available experimental data to support this criterion is far from enough. In the current study, the high-throughput ab initio modeling is applied to investigate the relative stability of FCC and BCC single crystals of the Al-Co-Cr-Fe-Ni high entropy alloys (HEAs) by using the special quasi-random structure (SQS) approach. Furthermore, the predictions start with pure elements of the Al-Co-Cr-Fe-Ni system and are continued with binaries, ternaries, and quaternary compositions, which come up with 180 compositions (360 structures). After that, the reliability of the VEC criterion is testified. The results show that the VEC criterion not only works for the stable structure but also works effectively for metastable structure when both FCC and BCC are not thermodynamic stable. However, it is found that the old VEC criterion proposed by Guo et al. fails to work effectively for compositions containing high concentrations of light-weight metals such as Al at VEC<5. To solve this problem, the present work proposes a new VEC rule to define the stability of FCC and BCC structures at the ground state. With the implementation of the new VEC rule, the effectiveness of the VEC rule (EVEC) of both FCC and BCC structures is enhanced, especially for pure elements and binary compositions, indicating that this rule does not only work effectively for multicomponent systems but also works for low-order systems.

36 MATERIALS SCIENCE↗

DOE OSTI2016

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

A new reference krypton-krypton interatomic potential energy curve was developed by means of quantum-chemical ab initio calculations for 36 interatomic separations. Highly accurate values for the interaction energies at the complete basis set limit were obtained using the coupled-cluster method with single, double, and perturbative triple excitations as well as t-aug-cc-pV5Z and t-aug-cc-pV6Z basis sets including mid-bond functions, with the 6Z basis set being newly constructed for this study. Higher orders of coupled-cluster terms were considered in a successive scheme up to full quadruple excitations. Core-core and core-valence correlation effects were included. Furthermore, relativistic effects were studied not only at a scalar relativistic level using second-order direct perturbation theory, but also utilizing full four-component and Gaunt-effect computations. An analytical pair potential function was fitted to the interaction energies, which is characterized by a depth of 200.88 K with an estimated standard uncertainty of 0.51 K. Thermophysical properties of low-density krypton were calculated for temperatures up to 5000 K. Second and third virial coefficients were obtained from statistical thermodynamics. Viscosity and thermal conductivity as well as the self-diffusion coefficient were computed using the kinetic theory of gases. The theoretical results are compared with experimental data and with results for other pair potential functions from the literature, especially with those calculated from the recently developed ab initio potential of Waldrop et al. [J. Chem. Phys. 142, 204307 (2015)]. Highly accurate experimental viscosity data indicate that both the present ab initio pair potential and the one of Waldrop et al. can be regarded as reference potentials, even though the quantum-chemical methods and basis sets differ. However, the uncertainties of the present potential and of the derived properties are estimated to be considerably lower.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Measuring 14 Elemental Abundances with R = 1800 LAMOST Spectra

The LAMOST survey has acquired low-resolution spectra (R = 1800) for 5 million stars across the Milky Way, far more than any current stellar survey at a corresponding or higher spectral resolution. It is often assumed that only very few elemental abundances can be measured from such low-resolution spectra, limiting their utility for Galactic archaeology studies. However, Ting et al. used ab initio models to argue that low-resolution spectra should enable precision measurements of many elemental abundances, at least in theory. Here, we verify this claim in practice by measuring the relative abundances of 14 elements from LAMOST spectra with a precision of ≲0.1 dex for objects with S/N{sub LAMOST}≳30 (per pixel). We employ a spectral modeling method in which a data-driven model is combined with priors that the model gradient spectra should resemble ab initio spectral models. This approach assures that the data-driven abundance determinations draw on physically sensible features in the spectrum in their predictions and do not just exploit astrophysical correlations among abundances. Our analysis is constrained to the number of elemental abundances measured in the APOGEE survey, which is the source of the training labels. Obtaining high quality/resolution spectra for a subset of LAMOST stars to measure more elemental abundances as training labels and then applying this method to the full LAMOST catalog will provide a sample with more than 20 elemental abundances, which is an order of magnitude larger than current high-resolution surveys, substantially increasing the sample size for Galactic archaeology.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Probing Few-Body Nuclear Dynamics via H 3 and He 3 ( e , e ' p ) pn Cross-Section Measurements

Here, we report the first measurement of the (e, e' p) three-body breakup reaction cross sections in helium-3 ( 3 He) and tritium ( 3 H) at large momentum transfer ($\langle{Q^2}\rangle$ ≈ 1.9 (GeV/c) 2 ) and x B > 1 kinematics, where the cross section should be sensitive to quasielastic (QE) scattering from single nucleons. The data cover missing momenta 40 ≤ p miss ≤ 500 MeV/c that, in the QE limit with no rescattering, equals the initial momentum of the probed nucleon. The measured cross sections are compared with state-of-the-art ab-initio calculations. Overall good agreement, within ±20%, is observed between data and calculations for the full p miss range for 3 H and for 100 ≤ p miss ≤ 350 MeV/c for 3 He. Including the effects of rescattering of the outgoing nucleon improves agreement with the data at p miss > 250 MeV/c and suggests contributions from charge-exchange (SCX) rescattering. The isoscalar sum of 3 He plus 3 H, which is largely insensitive to SCX, is described by calculations to within the accuracy of the data over the entire pmiss range. This validates current models of the ground state of the three-nucleon system up to very high initial nucleon momenta of 500 MeV/c.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2020

Temperature-dependent phonon lifetimes and thermal conductivity of silicon by inelastic neutron scattering and ab initio calculations

In this paper, inelastic neutron scattering on a single crystal of silicon was performed at temperatures from 100 to 1500 K. These experimental data were reduced to obtain phonon spectral intensity at all wave vectors $\overset{→}{Q}$ and frequencies ω in the first Brillouin zone. Thermal broadenings of the phonon peaks were obtained by fitting and by calculating with an iterative ab initio method that uses thermal atom displacements on an ensemble of superlattices. Agreement between the calculated and experimental broadenings was good, with possible discrepancies at the highest temperatures. Distributions of phonon widths versus phonon energy had similar shapes for computation and experiment. These distributions grew with temperature but maintained similar shapes. Parameters from the ab initio calculations were used to obtain the thermal conductivity from the Boltzmann transport equation, which was in good agreement with experimental data. Despite the high group velocities of longitudinal acoustic phonons, their shorter lifetimes reduced their contribution to the thermal conductivity, which was dominated by transverse acoustic modes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Uranus evolution models with simple thermal boundary layers

The strikingly low luminosity of Uranus (T eff ≃ T eq ) constitutes a long-standing challenge to our understanding of Ice Giant planets. Here we present the first Uranus structure and evolution models that are constructed to agree with both the observed low luminosity and the gravity field data. Here, our models make use of modern ab initio equations of state at high pressures for the icy components water, methane, and ammonia. Proceeding step by step, we confirm that adiabatic models yield cooling times that are too long, even when uncertainties in the ice:rock ratio (I:R) are taken into account. We then argue that the transition between the ice/rock-rich interior and the H/He-rich outer envelope should be stably stratified. Therefore, we introduce a simple thermal boundary and adjust it to reproduce the low luminosity. Due to this thermal boundary, the deep interior of the Uranus models are up to 2–3 warmer than adiabatic models, necessitating the presence of rocks in the deep interior with a possible I:R of 1 × solar. Finally, we allow for an equilibrium evolution (T eff ≃ T eq ) that begun prior to the present day, which would therefore no longer require the current era to be a ”special time” in Uranus’ evolution. In this scenario, the thermal boundary leads to more rapid cooling of the outer envelope. When T eff ≃ T eq is reached, a shallow, subadiabatic zone in the atmosphere begins to develop. Its depth is adjusted to meet the luminosity constraint. This work provides a simple foundation for future Ice Giant structure and evolution models, that can be improved by properly treating the heat and particle fluxes in the diffusive zones.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2024

Capturing the generation and structural transformations of molecular ions

Molecular ions are ubiquitous and play pivotal roles in many reactions, particularly in the context of atmospheric and interstellar chemistry. However, their structures and conformational transitions, particularly in the gas phase, are less explored than those of neutral molecules owing to experimental difficulties. A case in point is the halonium ions, whose highly reactive nature and ring strain make them short-lived intermediates that are readily attacked even by weak nucleophiles and thus challenging to isolate or capture before they undergo further reaction. Here we show that mega-electronvolt ultrafast electron diffraction (MeV-UED), used in conjunction with resonance-enhanced multiphoton ionization, can monitor the formation of 1,3-dibromopropane (DBP) cations and their subsequent structural dynamics forming a halonium ion. We find that the DBP + cation remains for a substantial duration of 3.6 ps in aptly named ‘dark states’ that are structurally indistinguishable from the DBP electronic ground state. The structural data, supported by surface-hopping simulations and ab initio calculations, reveal that the cation subsequently decays to iso-DBP + , an unusual intermediate with a four-membered ring containing a loosely bound bromine atom, and eventually loses the bromine atom and forms a bromonium ion with a three-membered-ring structure. We anticipate that the approach used here can also be applied to examine the structural dynamics of other molecular ions and thereby deepen our understanding of ion chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Stoner versus Heisenberg: Ultrafast exchange reduction and magnon generation during laser-induced demagnetization

Understanding how the electronic band structure of a ferromagnetic material is modified during laser-induced demagnetization on femtosecond timescales has been a long-standing question in condensed matter physics. Here, we use ultrafast high harmonics to measure time-, energy-, and angle-resolved M-edge magnetic asymmetry spectra for Co lms after optical pumping to induce ultrafast demagnetization. This provides a complete data set that we can compare with advanced ab initio magneto-optical calculations. Here, tur analysis identifies that the dominant mechanisms contributing to ultrafast demagnetization on timescales up to several picoseconds are a transient reduction in the exchange splitting and the excitation of ultrafast magnons. Surprisingly, we nd that the magnon contribution to ultrafast demagnetization is already strong on sub-picosecond timescales, while the reduction in exchange splitting persists to several picoseconds.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Unraveling the intrinsic atomic physics behind x-ray absorption line shifts in warm dense silicon plasmas

Here, we present a novel free-energy density functional theory (DFT)-based methodology for optical property calculations of warm dense matter to cover a wide range of thermodynamic conditions and photon energies including the entire x-ray range. It uses Mermin–Kohn–Sham density functional theory with exchange-correlation (XC) thermal effects taken into account via a fully temperature dependent generalized gradient approximation XC functional. The methodology incorporates a combination of the ab initio molecular dynamics (AIMD) snapshotted Kubo–Greenwood optic data with a single-atom in simulation cell calculations to close the photon energy gap between the L and K edges and extend the K-edge tail toward many-keV photon energies. This gap arises in the standard scheme due to a prohibitively large number of bands required for the Kubo–Greenwood calculations with AIMD snapshots. Kubo–Greenwood data on snapshots provide an accurate description of optic properties at low photon frequencies slightly beyond the L-edge and x-ray absorption near edges structure (XANES) spectra, while data from periodic calculations with single atoms cover the tail regions beyond the edges. To demonstrate its applicability to mid-Z materials where the standard DFT-based approach is not computationally feasible, we have applied it to opacity calculations of warm dense silicon plasmas. These first-principles calculations revealed a very interesting phenomon of red-to-blue shift in K–L (1s → 2p) and K-edge absorptions along both isotherm and isochore, which are absent in most continuum-lowering models of traditional plasma physics. This new physics phenomenon can be attributed to the underlying competition between the screening of deeply bound core electrons and the screening of outer-shell electrons caused by warm-dense-plasma conditions. We further demonstrate that the ratio of 1s → 2p to the K-edge x-ray absorptions can be used to characterize warm-dense-plasma conditions. Eventually, based on our absorption calculations, we have established a first-principles opacity table (FPOT) for silicon in a wide range of material densities and temperatures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

High-throughput electronic structure package

We introduce HTESP (High-Throughput Electronic Structure Package), an automated tool designed for high-throughput ab initio calculations. HTESP simplifies the entire workflow, including data extraction, input files generation, calculation submission, result collection, and plotting. The package is implemented in Python and Bash languages. In this paper, we provide detailed information about the package, its installation process and some illustrative examples to demonstrate its usage. Additionally, the package includes comprehensive online documentation on input parameters and tutorials to assist users.

Nepal, NirajK↗

DOE OSTI2025

An Overview of the Molten Salt Thermal Properties Database–Thermophysical, Version 4.0 (MSTDB-TP V.4.0)

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).

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS1989

Classical trajectory studies of gas phase reaction dynamics and kinetics using ab initio potential energy surfaces

Strategies for constructing global potential energy surfaces from a limited number of accurate ab initio electronic energy calculations are discussed. Generally, these data are concentrated in small regions of configuration space (e.g., in the vicinity of saddle points and energy minima) and difficulties arise in generating a potential function that is globally well-behaved. Efficient computer codes for carrying out classical trajectory calculations on vector and parallel processors are also described. Illustrations are given from recent work on the following chemical systems: Ca + HF yields CaF + H, H + H + H2 yields H2 + H2, N + O2 yields NO + O and O + N2 yields NO + N. The dynamics and kinetics of metathesis, dissociation, recombination, energy transfer and complex formation processes will be discussed.

Jaffe, Richard L.↗

NASA NTRS1997

Rotational Energy Transfer of N2 Determined Using a New Ab Initio Potential Energy Surface

A new N2-N2 rigid-rotor surface has been determined using extensive Ab Initio quantum chemistry calculations together with recent experimental data for the second virial coefficient. Rotational energy transfer is studied using the new potential energy surface (PES) employing the close coupling method below 200 cm(exp -1) and coupled state approximation above that. Comparing with a previous calculation based on the PES of van der Avoird et al.,3 it is found that the new PES generally gives larger cross sections for large (delta)J transitions, but for small (delta)J transitions the cross sections are either comparable or smaller. Correlation between the differences in the cross sections and the two PES will be attempted. The computed cross sections will also be compared with available experimental data.

Huo, Winifred M.↗