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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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DOE OSTI2026

Data for The impact of aerosol mixing state on immersion freezing: Insights from classical nucleation theory and particle-resolved simulations

This dataset contains the values directly shown in the figures of the article "The impact of aerosol mixing state on immersion freezing: Insights from classical nucleation theory and particle-resolved simulations". This article is in preparation for submission to the journal Atmospheric Chemistry and Physics. The dataset consists of 12 NetCDF files processed from the raw output of the PartMC model. It does not include the theoretical values of frozen fraction, which can be computed using the equations provided in the paper. *New in V2: adding data for a newly included figure (INP_spectrum.nc), removing files that are no longer used in the revised manuscript figures (e.g., UNC_A_ratio=0.9_Dp=0.1.nc, UNC_A_ratio=0.9_Dp=10.0.nc, UNC_A_ratio=0.1_Dp=0.1.nc, and UNC_A_ratio=0.1_Dp=10.0.nc), and updating README.pdf accordingly.

Aerosol mixing state↗

DOE OSTI2025

ChemComp: A Compilation Framework for Computing with Chemical Reaction Networks

The acceleration of scientific computation, data analytics, and artificial intelligence is driving a surge in computational requirements. Yet, state-of-the-art high-performance computing systems are approaching physical limitations that impede further significant improvements in energy efficiency. As we move towards post-exascale computing systems, innovative approaches are necessary to overcome this barrier in power consumption. Novel analog and hybrid digital-analog architectures hold promise for enhancing energy efficiency by several orders of magnitude. Biochemical computation stands out among the various solutions being explored due to its potential to enable new classes of devices with immense computational capabilities. These devices can capitalize on the inherent efficacy of biological cells in solving optimization problems and are scalable through increasing reaction system size or vessel capacity, potentially satisfying scientific computing's high-performance requirements. Nonetheless, several theoretical and practical limitations persist, including problem formulation and mapping to chemical reaction networks (CRNs) and implementation of actual CRN devices. In this paper, we propose a framework for biochemical computation using systems chemistry. We present the initial components of our approach: an abstract chemical reaction dialect implemented as a multi-level intermediate representation (MLIR) compiler extension and a pathway to represent mathematical problems with CRNs. To showcase the potential of this approach, we emulate a simplified chemical reservoir device. This work lays the groundwork for leveraging chemistry's computing potential in creating energy-efficient, high-performance computing systems tailored to contemporary computational needs.

artificial intelligence↗

DOE OSTI2021

In Silico Discovery of Multistep Chemistry Initiated by a Conical Intersection: The Challenging Case of Donor–Acceptor Stenhouse Adducts

Detailed mechanistic understanding of multistep chemical reactions triggered by internal conversion via a conical intersection is a challenging task that emphasizes limitations in theoretical and experimental techniques. We present a discovery-based, hypothesis-free computational approach based on first-principles molecular dynamics to discover and refine the switching mechanism of donor–acceptor Stenhouse adducts (DASAs). We simulate the photochemical experiment in silico, following the “hot” ground state dynamics for 10 ps after photoexcitation. Using state-of-the-art graphical processing units-enabled electronic structure calculations we performed in total ~2 ns of nonadiabatic ab initio molecular dynamics discovering (a) critical intermediates that are involved in the open-to-closed transformation, (b) several competing pathways which lower the overall switching yield, and (c) key elements for future design strategies. Finally, our dynamics describe the natural evolution of both the nuclear and electronic degrees of freedom that govern the interconversion between DASA ground-state intermediates, exposing significant elements for future design strategies of molecular switches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

InteraChem: Virtual Reality Visualizer for Reactive Interactive Molecular Dynamics

Interactive molecular dynamics in virtual reality (IMD-VR) simulations provide a digital molecular playground for students as an alternative or complement to traditional molecular modeling kits or 2D illustrations. Previous IMD-VR studies have used molecular mechanics to enable simulations of macromolecules such as proteins and nanostructures for the classroom setting with considerable success. Here, we present the InteraChem molecular visualizer, intended for reactive IMD-VR simulation using semiempirical and ab initio methods. InteraChem visualizes not only the molecular geometry but also (1) isosurfaces such as molecular orbitals and electrostatic potentials and (2) two-dimensional graphs of time-varying simulation quantities such as kinetic/potential energy, internal coordinates, and user-applied force. Additionally, InteraChem employs speech recognition to facilitate user interaction and introduces a novel “atom happiness” visualization using emojis to indicate the energetic feasibility of a particular bonding arrangement. Furthermore, we include a set of accompanying exercises that we have used to teach chemical reactivity in small molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

On the Efficient Evaluation of the Exchange Correlation Potential on Graphics Processing Unit Clusters

The predominance of Kohn–Sham density functional theory (KS-DFT) for the theoretical treatment of large experimentally relevant systems in molecular chemistry and materials science relies primarily on the existence of efficient software implementations which are capable of leveraging the latest advances in modern high-performance computing (HPC). With recent trends in HPC leading toward increasing reliance on heterogeneous accelerator-based architectures such as graphics processing units (GPU), existing code bases must embrace these architectural advances to maintain the high levels of performance that have come to be expected for these methods. In this work, we purpose a three-level parallelism scheme for the distributed numerical integration of the exchange-correlation (XC) potential in the Gaussian basis set discretization of the Kohn–Sham equations on large computing clusters consisting of multiple GPUs per compute node. In addition, we purpose and demonstrate the efficacy of the use of batched kernels, including batched level-3 BLAS operations, in achieving high levels of performance on the GPU. We demonstrate the performance and scalability of the implementation of the purposed method in the NWChemEx software package by comparing to the existing scalable CPU XC integration in NWChem.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1986

Physics through the 1990s: Scientific interfaces and technological applications

The volume examines the scientific interfaces and technological applications of physics. Twelve areas are dealt with: biological physics-biophysics, the brain, and theoretical biology; the physics-chemistry interface-instrumentation, surfaces, neutron and synchrotron radiation, polymers, organic electronic materials; materials science; geophysics-tectonics, the atmosphere and oceans, planets, drilling and seismic exploration, and remote sensing; computational physics-complex systems and applications in basic research; mathematics-field theory and chaos; microelectronics-integrated circuits, miniaturization, future trends; optical information technologies-fiber optics and photonics; instrumentation; physics applications to energy needs and the environment; national security-devices, weapons, and arms control; medical physics-radiology, ultrasonics, MNR, and photonics. An executive summary and many chapters contain recommendations regarding funding, education, industry participation, small-group university research and large facility programs, government agency programs, and computer database needs.

Source record↗

DOE OSTI2022

Diffusion Monte Carlo approaches for studying nuclear quantum effects in fluxional molecules

Abstract Diffusion quantum Monte Carlo (DMC) provides a powerful approach for obtaining the ground state energy and wave function of molecules, ions, and molecular clusters. The approach is uniquely well suited for studies of fluxional molecules, which undergo large amplitude vibrational motions even in their ground state. In contrast to the electronic structure problem, where the wave function must be antisymmetric with respect to exchange of any pair of electrons, the wave function for the ground vibrational state is nodeless. This greatly simplifies the application of DMC for vibrational problems. Because there is not a single potential function that can be used to describe the intramolecular and intermolecular interactions in all molecular systems, most methods that are used to describe nuclear quantum effects rely on a carefully chosen zero‐order description of the molecular vibrations. In contrast, DMC calculations can be performed in Cartesian coordinates, making the DMC algorithm easily transferable between different chemical systems. In this contribution, the theory that underlies DMC will be discussed along with important considerations for performing DMC calculations. Extensions for evaluating vibrationally excited states and molecular properties are also discussed. Insights that can be obtained from DMC calculations are illustrated in the context of the protonated water clusters. This article is categorized under: Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods Theoretical and Physical Chemistry > Spectroscopy

Chemistry↗

DOE OSTI2020

Toward DMRG-tailored coupled cluster method in the 4c-relativistic domain

There are three essential problems in computational relativistic chemistry: Electrons moving at relativistic speeds, close lying states, and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules in which all the three effects are present. These are the heavier transition metal compounds, lanthanides, and actinides with open d or f shells. For such systems, sufficiently accurate numerical methods are not available, which hinders the application of theoretical chemistry in this field. In this paper, we combine two numerical methods in order to address this challenging class of molecules. These are the relativistic versions of coupled cluster methods and the density matrix renormalization group (DMRG) method. To the best of our knowledge, this is the first relativistic implementation of the coupled cluster method externally corrected by DMRG. The method brings a significant reduction of computational costs as we demonstrate on the system of TlH, AsH, and SbH.

Brandejs, Jan (ORCID:0000000221073095)↗

DOE OSTI2023

Active Thermochemical Tables: Enthalpies of Formation of Bromo- and Iodo-Methanes, Ethenes and Ethynes

Here, the thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new Feller–Peterson–Dixon (FPD) style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the Active Thermochemical Tables (ATcT). From the computational viewpoint, a slower convergence of the components of composite thermochemistry methods is observed relative to species that solely contain first row elements, leading to a higher computational expense for achieving comparable levels of accuracy. Potential systematic sources of computational uncertainty are investigated, and, not surprisingly, spin-orbit coupling is found to be a critical component, particularly for iodine containing molecular species. The ATcT analysis of available experimental and theoretical determinations indicates that prior theoretical determinations have significantly larger uncertainties than originally reported, particularly in cases where molecular spin-orbit effects were ignored. Accurate and reliable heats of formation are reported for 38 halogen containing systems, based on combining the current computations with previous experimental and theoretical work via the ATcT approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Real-space Kohn–Sham density functional theory for complex energy applications

Real-space Kohn-Sham density functional theory (real-space KS-DFT) enables large-scale electronic structure simulations that is particularly well-suited for the modern high-performance computing (HPC) architectures. This feature article reviews its theoretical foundations, highlights the algorithmic advances and recent developments, and showcases applications in complex nano systems. We aim to provide a perspective on the trajectory of real-space KS-DFT as an emerging tool for computational chemistry and materials science in the exascale era.

Zhang, Zeyi↗

NASA NTRS2005

Rare Gases Inserted into Biological Building Blocks: A Theoretical Study of Glycine - Rg Compounds (Rg-Xe, Kr, Ar)

Compounds formed by insertion of rare-gas atoms (Xe, Kr, and Ar) into glycine molecule are investigated using accurate ab initio computational methods. Identification of such insertion compounds may open new frontiers in the field of rare-gas chemistry, such as possible existence of biological molecules that include chemically bound rare gas atoms. The most stable glycine-Rg configuration is found to correspond to insertion of Rg atoms into the 0-H bond of glycine. These NH2CH2COORgH compounds are metastable , but separated by sizable potential barriers from the Rg + glycine dissociation products. Preliminary calculations show that NH2CH2COOXeH compound is energetically stable with respect to another (3-body) dissociation channel (NH2CH2COO + Rg + H), while the corresponding Ar species is not stable in this respect. The compound with the inserted Kr is a borderline case, with the 3-body dissociation products being close in energy to the NH2CH2COOKrH minimum.

Chaban, Galina M.↗

DOE OSTI2024

Assembly of short amphiphilic peptoids into nanohelices with controllable supramolecular chirality

Abstract A long-standing challenge in bioinspired materials is to design and synthesize synthetic materials that mimic the sophisticated structures and functions of natural biomaterials, such as helical protein assemblies that are important in biological systems. Herein, we report the formation of a series of nanohelices from a type of well-developed protein-mimetics called peptoids. We demonstrate that nanohelix structures and supramolecular chirality can be well-controlled through the side-chain chemistry. Specifically, the ionic effects on peptoids from varying the polar side-chain groups result in the formation of either single helical fiber or hierarchically stacked helical bundles. We also demonstrate that the supramolecular chirality of assembled peptoid helices can be controlled by modifying assembling peptoids with a single chiral amino acid side chain. Computational simulations and theoretical modeling predict that minimizing exposure of hydrophobic domains within a twisted helical form presents the most thermodynamically favorable packing of these amphiphilic peptoids and suggests a key role for both polar and hydrophobic domains on nanohelix formation. Our findings establish a platform to design and synthesize chiral functional materials using sequence-defined synthetic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Symmetry dilemmas in quantum computing for chemistry: A comprehensive analysis

Symmetry adaptation, universality, and gate efficiency are central but often competing requirements in quantum algorithms for electronic structure and many-body physics. For example, fully symmetry-adapted universal operator pools typically generate long and deep quantum circuits; gate-efficient universal operator pools generally break symmetries; and gate-efficient, fully symmetry-adapted operator pools may not be universal. In this work, we analyze such symmetry dilemmas both theoretically and numerically. On the theory side, we prove that the popular, gate-efficient operator pool consisting of singlet spin-adapted singles and perfect-pairing doubles is not universal when spatial symmetry is enforced. To demonstrate the strengths and weaknesses of the three types of pools, we perform numerical simulations using an adaptive algorithm paired with operator pools that are (i) fully symmetry-adapted and universal, (ii) fully symmetry-adapted and non-universal, and (iii) breaking a single symmetry and universal. Our numerical simulations encompass three physically relevant scenarios in which the target state is (i) the global ground state, (ii) the ground state crossed by a state differing in multiple symmetry properties, and (iii) the ground state crossed by a state differing in a single symmetry property. Our results show when symmetry-breaking but universal pools can be used safely, when enforcing at least one distinguishing symmetry suffices, and when a particular symmetry must be rigorously preserved to avoid variational collapse. Together, the formal and numerical analyses provide a practical guide for designing and benchmarking symmetry-adapted operator pools that balance universality, resource requirements, and robust state targeting in quantum simulations for chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Strangely attractive: Collaboration and feedback in the field of molecular magnetism

The fluid synergy between experimentalists and theoreticians has, for decades, led to a deeper understanding of the processes that govern single-molecule magnets. This approach has allowed for the establishment of proven design criteria for the control of magnetic properties through molecular architecture and the development of new magnetic measurement techniques and innovative computational methodologies. Here, we give an account of the experimental and theoretical joint endeavor carried out as part of the synthesis group led by David Mills and the computational/theoretical team led by Nicholas Chilton, together with colleagues in synthetic f-element chemistry and magnetism at the University of Manchester. In addition, we provide a personal perspective on collaborative work in molecular magnetism and how such collaborations are essential for advancing the field further.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Association Kinetics for Perfluorinated n -Alkyl Radicals

Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched n-perfluoroalkyl chains, and their corresponding reverse barrierless association reactions, are expected to be significant contributors to the gas-phase thermal decomposition of families of species such as perfluorinated carboxylic acids and perfluorinated sulfonic acids. Unfortunately, experimental data for these reactions are scarce and uncertain. Furthermore, obtaining reliable theoretical predictions for such reactions is a laborious and computationally intensive task. Here, in this work, the chemical kinetics of the various association/decomposition reactions producing/decomposing the C 2 -C 4 series of unbranched n-perfluoroalkanes (C 2 F 6 , C 3 F 8 , and C 4 F 10 ) are examined using state-of-the-art ab initio transition-state-theory-based master-equation calculations. The variable-reaction-coordinate transition-state theory (VRC-TST) formalism is employed in computing the microcanonical and canonical rates for the association reactions. Reaction thermochemistry is obtained via composite quantum chemistry calculations and the laddering of error-canceling reaction schemes via a connectivity-based hierarchy approach employing ANL1/ANL0-style reference energies. Lennard-Jones collision model parameters for the considered systems were estimated by a direct dynamics approach, and collisional energy transfer parameters were obtained from analogies to systems of similar size and heavy-atom connectivity. A one-dimensional master equation approach was used to convert the microcanonical rate coefficients from the VRC-TST analysis into temperature- and pressure-dependent rate constants for the association reactions and the reverse dissociation reactions. The data are reported in standardized formats for usage in comprehensive chemical kinetic models for PFAS thermal destruction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1990

Theoretical investigation of non-equilibrium chemistry and optical radiation in hypersonic flow fields

Future space vehicles returning from distant missions or high earth orbits may enter the upper regions of the atmosphere and use aerodynamic drag to reduce their velocity before they skip out of the atmosphere and enter low earth orbit. The Aeroassist Flight Experiment (AFE) is designed to explore the special problems encountered in such entries. A computer code was developed to calculate the radiative transport along line-or-sight in the general 3-D flow field about an arbitrary entry vehicle, if the temperatures and species concentrations along the line-of-sight are known. The radiative heating calculation at the stagnation point of the AFE vehicle along the entry trajectory was performed, including a detailed line-by-line accounting of the radiative transport in the vacuum ultraviolet (below 200 nm) by the atomic N and O lines. A method was developed for making measurements of the haze particles in the Titan atmosphere above 200 km altitude. Several other tasks of a continuing nature, to improve the technical ability to calculate the nonequilibrium gas dynamic flow field and radiative heating of entry vehicles, were completed or advanced.

Whiting, Ellis E.↗

DOE OSTI2023

Nanoscale Surface Structure of Nanometer-Thick Ferroelectric BaTiO 3 Films Revealed by Synchrotron X-ray Scanning Tunneling Microscopy: Implications for Catalytic Adsorption Reactions

Ferroelectric nanomaterials are of interest in catalysis, non-volatile memory, and neuromorphic computing among other applications because of their switchable structure that can alter electronic and interface properties of a single material. The investigation of the role of polarization on the surface structure and chemistry of ferroelectric nanomaterials is a longstanding challenge, as it ideally requires a combination of both nanoscale imaging and chemical spectroscopy. In this work we study a model ferroelectric BaTiO 3 thin film by synchrotron X-ray scanning tunneling microscopy (SX-STM), a unique method which integrates nanoscale surface imaging and chemically sensitive spectroscopy. We find that polarization switching from downward to upward in (001)single crystalline BaTiO 3 thin films increases the intensity of X-ray absorption across Ba M, Ti L and O K edges. Chemical mapping of nanometer sized domains further demonstrates the modulation of surface structures upon polarization switching, as well as confirming the trends observed in single point experiments across the surface. Here, we complement these measurements with ab-initio computational absorption spectroscopy to elucidate the effect of polarization switching on the core-hole excitations using the Bethe-Salpeter equation approach. Our experimental and theoretical results thus confirm a stronger binding strength for the upward polarized surface with molecular O 2 as a model reactant, offering mechanistic evidence that supports previous reports. This work advances the understanding of the surface chemistry and electronic structure of ferroelectrics, which can ultimately aid strategies to design interfaces with tailored properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2022

Tuning chemical precompression: Theoretical design and crystal chemistry of novel hydrides in the quest for warm and light superconductivity at ambient pressures

Over the past decade, a combination of crystal structure prediction techniques and experimental synthetic work has thoroughly explored the phase diagrams of binary hydrides under pressure. The fruitfulness of this dual approach is demonstrated in the recent identification of several superconducting hydrides with T c s approaching room temperature. We start with an overview of the computational procedures for predicting stable structures and estimating their propensity for superconductivity. A survey of phases with high T c reveals some common structural features that appear conducive to the strong coupling of the electronic structure with atomic vibrations that leads to superconductivity. We discuss the stability and superconducting properties of phases containing two of these—molecular H 2 units mixed with atomic H and hydrogenic clathrate-like cages—as well as more unique motifs. Lastly, we argue that ternary hydride phases, whose exploration is still in its infancy, are a promising route to achieve simultaneous superconductivity at high temperatures and stability at low pressures. Several ternary hydrides arise from the addition of a third element to a known binary hydride structure through site mixing or onto a new site, and several more are based on altogether new structural motifs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗