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DOE OSTI2026

Insights into the Reactivity of Brookite TiO 2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Brookite TiO 2 , a rare natural polymorph of TiO 2 , has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (O br H) and terminal hydroxyls (Ti –OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti 3+ ) sites, while Ti –OH groups prefer to form at the four-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

1q21.1 distal copy number variants are associated with cerebral and cognitive alterations in humans

Low-frequency 1q21.1 distal deletion and duplication copy number variant (CNV) carriers are predisposed to multiple neurodevelopmental disorders, including schizophrenia, autism and intellectual disability. Human carriers display a high prevalence of micro- and macrocephaly in deletion and duplication carriers, respectively. The underlying brain structural diversity remains largely unknown. We systematically called CNVs in 38 cohorts from the large-scale ENIGMA-CNV collaboration and the UK Biobank and identified 28 1q21.1 distal deletion and 22 duplication carriers and 37,088 non-carriers (48% male) derived from 15 distinct magnetic resonance imaging scanner sites. With standardized methods, we compared subcortical and cortical brain measures (all) and cognitive performance (UK Biobank only) between carrier groups also testing for mediation of brain structure on cognition. We identified positive dosage effects of copy number on intracranial volume (ICV) and total cortical surface area, with the largest effects in frontal and cingulate cortices, and negative dosage effects on caudate and hippocampal volumes. The carriers displayed distinct cognitive deficit profiles in cognitive tasks from the UK Biobank with intermediate decreases in duplication carriers and somewhat larger in deletion carriers—the latter potentially mediated by ICV or cortical surface area. These results shed light on pathobiological mechanisms of neurodevelopmental disorders, by demonstrating gene dose effect on specific brain structures and effect on cognitive function.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2022

Ultrafast infrared transient absorption spectroscopy of gas-phase Ni(CO) 4 photodissociation at 261 nm

Here, we employ ultrafast mid-infrared transient absorption spectroscopy to probe the rapid loss of carbonyl ligands from gas-phase nickel tetracarbonyl following ultraviolet photoexcitation at 261 nm. Here, nickel tetracarbonyl undergoes prompt dissociation to produce nickel tricarbonyl in a singlet excited state; this electronically excited tricarbonyl loses another CO group over tens of picoseconds. Our results also suggest the presence of a parallel, concerted dissociation mechanism to produce nickel dicarbonyl in a triplet excited state, which likely dissociates to nickel monocarbonyl. Mechanisms for the formation of these photoproducts in multiple electronic excited states are theoretically predicted with one-dimensional cuts through the potential energy surfaces and computation of spin–orbit coupling constants using equation of motion coupled cluster methods (EOM-CC) and coupled cluster theory with single and double excitations (CCSD). Bond dissociation energies are calculated with CCSD, and anharmonic frequencies of ground and excited state species are computed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces

The creation of stable molecular monolayers on metallic surfaces is a fundamental challenge of surface chemistry. N-Heterocyclic carbenes (NHCs) were recently shown to form self-assembled monolayers that are significantly more stable than the traditional thiols on Au system. In this study, we theoretically and experimentally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly than NHCs to Au surfaces without altering the surface structure. We deposit bis(diisopropylamino)cyclopropenylidene (BAC) on Au(111) using the molecular adduct BAC–CO 2 as a precursor and determine the structure, geometry, and behavior of the surface-bound molecules through high-resolution X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Our experiments are supported by density functional theory calculations of the molecular binding energy of BAC on Au(111) and its electronic structure. Our work is the first demonstration of surface modification with a stable carbene other than NHC; more broadly, it drives further exploration of various carbenes on metal surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

Arsenic Fate in Peat Controlled by the pH-Dependent Role of Reduced Sulfur

Reduced sulfur (S) has a contrasting role in the fate of arsenic (As) in peatlands. Sulfur bridges provide efficient binding of As to organic carbon (C), but the formation of aqueous As–S species, so-called thioarsenates, leads to a low to no sorption tendency to organic C functional groups. Here, we studied how pH changes the role of reduced S in desorption and retention of presorbed As in model peat. Control desorption experiments without S addition revealed that As was mobilized, predominantly as arsenite, in all treatments with relative mobilization increasing with pH (4.5 < 7.0 < 8.5). Addition of sulfide or polysulfide caused substantial As retention at acidic conditions but significantly enhanced As desorption compared to controls at neutral to alkaline pH. Thioarsenates dominated As speciation at pH 7.0 and 8.5 (maximum, 79%) and remained in solution without (re)sorption to peat. Predominance of arsenite in control experiments and no evidence of surface-bound thioarsenates at pH 7.0 suggest mobilization to proceed via arsenite desorption, reaction with dissolved or surface-bound reduced S, and formation of thioarsenates. Our results suggest that natural or management-related increases in pH or increases in reduced S in near-neutral pH environments can turn organic matter from an As sink into a source.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1990

Surface and airborne evidence for plumes and winds on Triton

Aeolian features on Triton that were imaged during the Voyager Mission have been grouped. The term 'aeolian feature' is broadly defined as features produced by or blown by the wind, including surface and airborne materials. Observations of the latitudinal distributions of the features probably associated with current activity (known plumes, crescent streaks, fixed terminator clouds, and limb haze with overshoot) all occur from latitude -37 deg to latitude -62 deg. Likely indicators of previous activity (dark surface streaks) occur from latitude -5 deg to -70 deg, but are most abundant from -15 deg to -45 deg, generally north of currently active features. Those indicators which give information on wind direction and speed have been measured. Wind direction is a function of altitude. The predominant direction of the surface wind streaks is found to be between 40 deg and 80 deg measured clockwise from north. The average orientation of streaks in the northeast quadrant is 59 deg. Winds at 1- to 3-kilometer altitude are eastward, while those at more than 8 kilometers blow west.

Hansen, C. J.↗

DOE OSTI2020

The MATHUSLA test stand

The rate of muons from LHC pp collisions reaching the surface above the ATLAS interaction point is measured as a function of the ATLAS luminosity and compared with expected rates from decays of W and Z bosons and b- and c- quark jets. In addition, data collected during periods without beams circulating in the LHC provide a measurement of the background from cosmic ray inelastic backscattering that is compared to simulation predictions. Data were recorded during 2018 in a 2.5 × 2.5 × 6.5 m 3 active volume MATHUSLA test stand detector unit consisting of two scintillator planes, one at the top and one at the bottom, which defined the trigger, and six layers of RPCs between them, grouped into three ( x, y )-measuring layers separated by 1.74 m from each other. Triggers selecting both upward-going tracks and downward-going tracks were used.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2025

Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis

Metal–sulfur active sites play a central role in catalytic processes such as hydrogenation and dehydrogenation, yet the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, limiting overall efficiency. Here we present a strategy to embed metal–sulfur active sites into metal–organic frameworks (MOFs) by converting bridging or terminal chloride ligands into hydroxide and subsequently into sulfide groups through post-synthetic modification. We apply this method to two representative MOF families: one featuring one-dimensional metal–chloride chains and another containing discrete multinuclear metal clusters. Crystallographic and spectroscopic analyses confirm structural integrity and sulfide incorporation, and the transformation is monitored by in situ total scattering methods. The sulfided MOFs display enhanced catalytic activity in the selective hydrogenation of nitroarenes using molecular hydrogen. Density functional theory calculations indicate that sulfur incorporation promotes homolytic metal–ligand bond cleavage and facilitates H 2 activation. This work establishes an approach to construct MOFs featuring accessible metal–sulfide sites.

Catalyst synthesis↗

DOE OSTI2020

Dispersion of surface-modified, aggregated, fumed silica in polymer nanocomposites

Surface modification of model silica to enhance compatibility in nanocomposites has been widely studied. In addition to model spherical silica, several authors have investigated the impact of surface conditions on compatibility in commercial aggregated carbon black and silica. Here, dispersion is investigated for a series of nanocomposites produced from commercially modified fumed silica mixed with styrene butadiene rubber, polystyrene, and polydimethylsiloxane. Surface modification includes variation in surface hydroxyl content, siloxane, and silane treatment. Qualitatively, hydroxyl groups on the silica surface are considered incompatible with non-polar polymers, while methyl groups are compatible with oleophilic polymers. X-ray scattering was used to analyze the filler aggregate structure before and after dispersion, and the second virial coefficient was used to quantify nanodispersion. The content of surface moieties was determined from Fourier-transform infrared spectroscopy. It is observed that modified silica can display mean field or specific interactions as reflected by the presence of a correlation peak in x-ray scattering. For systems with specific interactions, a critical ordering concentration is observed related to the free energy change for structuring. A van der Waals model was used to model the second virial coefficient as a function of accumulated strain, yielding the excluded volume and an energetic term. The excluded volume could be predicted from the structural information, and the bound polymer layer was directly related to the surface methyl content, whereas the energetic term was found to synergistically depend on both the methyl and hydroxyl surface content.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Correlations between triaxial shapes and formation history of dark matter haloes

ABSTRACT The shape of dark matter (DM) haloes plays a critical role in constraining cosmology with upcoming large-scale structure surveys. In this paper, we study the correlations between the triaxial shapes and formation histories in DM haloes in the MultiDark Planck 2 N-body cosmological simulation. We find that halo ellipticity is strongly correlated with halo properties that serve as proxies of halo formation history, such as halo concentration and the normalized peak-centroid offset. These correlations are nearly independent of the halo density peak height. We present a simple model for the correlation between halo ellipticity and concentration using conditional abundance matching, and provide fitting formulae for the multidimensional distributions of triaxial halo shape as a function of halo peak height. We apply our halo shape model to gauge the effects of halo ellipticity and orientation bias on the excess surface mass density profiles in cluster-sized haloes. Our model should be useful for exploring the impact of triaxial halo shape on cosmological constraints in upcoming weak lensing surveys of galaxy clusters.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2021

Interfacial charge transfer and interaction in the MXene/TiO 2 heterostructures

Hybrid materials of MXenes [two-dimensional (2D) carbides and nitrides] and transition-metal oxides have shown great promise in electrical energy storage (EES) and 2D heterostructures have been proposed as the next-generation electrode materials to expand the limits of current technology. Here we use first principles density functional theory to investigate the interfacial structure, energetics, and electronic properties of the heterostructures of MXenes (Ti n+1 C n T 2 ; T = terminal groups) and anatase TiO 2 . We find that the greatest work-function differences are between OH-terminated MXene (1.6 eV) and anatase TiO 2 (101) (6.4 eV), resulting in the largest interfacial electron transfer (~0.9e/nm 2 across the interface) from MXene to the TiO 2 layer. This interface also has the strongest adhesion and is further strengthened by hydrogen bond formation. For O–, F–, or mixed O–/F– terminated Ti n+1 C n MXenes, electron transfer is minimal and interfacial adhesion is weak for their heterostructures with TiO 2 . The strong dependence of the interfacial properties of the MXene/TiO 2 heterostructures on the surface chemistry of the MXenes will be useful to tune the heterostructures for EES applications.

2-dimensinal systems↗

NASA NTRS2010

Systems Engineering and Reusable Avionics

One concept for future space flights is to construct building blocks for a wide variety of avionics systems. Once a unit has served its original purpose, it can be removed from the original vehicle and reused in a similar or dissimilar function, depending on the function blocks the unit contains. For example: Once a lunar lander has reached the moon's surface, an engine controller for the Lunar Decent Module would be removed and used for a lunar rover motor control unit or for a Environmental Control Unit for a Lunar Habitat. This senior design project included the investigation of a wide range of functions of space vehicles and possible uses. Specifically, this includes: (1) Determining and specifying the basic functioning blocks of space vehicles. (2) Building and demonstrating a concept model. (3) Showing high reliability is maintained. The specific implementation of this senior design project included a large project team made up of Systems, Electrical, Computer, and Mechanical Engineers/Technologists. The efforts were made up of several sub-groups that each worked on a part of the entire project. The large size and complexity made this project one of the more difficult to manage and advise. Typical projects only have 3-4 students, but this project had 10 students from five different disciplines. This paper describes the difference of this large project compared to typical projects, and the challenges encountered. It also describes how the systems engineering approach was successfully implemented so that the students were able to meet nearly all of the project requirements.

Conrad, James M.↗

NASA NTRS2015

System-Oriented Runway Management Concept of Operations

This document describes a concept for runway management that maximizes the overall efficiency of arrival and departure operations at an airport or group of airports. Specifically, by planning airport runway configurations/usage, it focuses on the efficiency with which arrival flights reach their parking gates from their arrival fixes and departure flights exit the terminal airspace from their parking gates. In the future, the concept could be expanded to include the management of other limited airport resources. While most easily described in the context of a single airport, the concept applies equally well to a group of airports that comprise a metroplex (i.e., airports in close proximity that share resources such that operations at the airports are at least partially dependent) by including the coordination of runway usage decisions between the airports. In fact, the potential benefit of the concept is expected to be larger in future metroplex environments due to the increasing need to coordinate the operations at proximate airports to more efficiently share limited airspace resources. This concept, called System-Oriented Runway Management (SORM), is further broken down into a set of airport traffic management functions that share the principle that operational performance must be measured over the complete surface and airborne trajectories of the airport's arrivals and departures. The "system-oriented" term derives from the belief that the traffic management objective must consider the efficiency of operations over a wide range of aircraft movements and National Airspace System (NAS) dynamics. The SORM concept is comprised of three primary elements: strategic airport capacity planning, airport configuration management, and combined arrival/departure runway planning. Some aspects of the SORM concept, such as using airport configuration management1 as a mechanism for improving aircraft efficiency, are novel. Other elements (e.g., runway scheduling, which is a part of combined arrival/departure runway scheduling) have been well studied, but are included in the concept for completeness and to allow the concept to define the necessary relationship among the elements. The goal of this document is to describe the overall SORM concept and how it would apply both within the NAS and potential future Next Generation Air Traffic System (NextGen) environments, including research conducted to date. Note that the concept is based on the belief that runways are the primary constraint and the decision point for controlling efficiency, but the efficiency of runway management must be measured over a wide range of space and time. Implementation of the SORM concept is envisioned through a collection of complementary, necessary capabilities collectively focused on ensuring efficient arrival and departure traffic management, where that efficiency is measured not only in terms of runway efficiency but in terms of the overall trajectories between parking gates and transition fixes. For the more original elements of the concept-airport configuration management-this document proposes specific air traffic management (ATM) decision-support automation for realizing the concept.

Lohr, Gary W.↗

NASA NTRS2018

Nature of and Lessons Learned from Lunar Ice Cube and the First Deep Space Cubesat 'Cluster'

Cubesats operating in deep space face challenges Earth-orbiting cubesats do not. 15 deep space cubesat 'prototypes' will be launched over the next two years including the two MarCO cubesats, the 2018 demonstration of dual communication system at Mars, and the 13 diverse cubesats being deployed from the SLS EM1 mission within the next two years. Three of the EM1 cubesat missions, including the first deep space cubesat 'cluster', will be lunar orbiters with remote sensing instruments for lunar surface/regolith measurements. These include: Lunar Ice Cube, with its 1-4 micron broadband IR spectrometer, BIRCHES, to determine volatile distribution as a function of time of day; Lunar Flashlight, to confirm the presence of surface ice at the lunar poles, utilizing an active source (laser), and looking for absorption features in the returning signal; and LunaH-Map to characterize ice at or below the surface at the poles with a compact neutron spectrometer. In addition, the BIRCHES instrument on Lunar Ice Cube will provide the first demonstration of a microcryocooler (AIM/IRIS) in deep space. Although not originally required to do so, all will be delivering science data to the Planetary Data System, the first formal archiving effort for cubesats. 4 of the 20 recently NASA-sponsored (PSDS3) study groups for deep space cubesat/smallsat mission concepts were lunar mission concepts, most involving 12U cubesats. NASA SIMPLEX 2/SALMON 3 AO will create ongoing opportunities for low-cost missions as 'rides' on government space program or private sector vehicles as these become available.

Ice Cube↗

NASA NTRS2018

Nature of and Lessons Learned from Lunar Ice Cube and the First Deep Space Cubesat 'Cluster'

Bujold, Emily↗

DOE OSTI2024

Sulfonated polybenzimidazole membrane with graphene oxide additive for 2,3-butanediol/water separation: A molecular simulation

Membrane separation for 2,3-butanediol (2,3-BDO) recovery from fermentation broth is highly valued for sustainable and renewable processes, but it requires efficient membrane materials. Here, this work evaluates the sulfonated polybenzimidazole (sPBI) and its graphene oxide (GO) doped composite membrane for separating 2,3-BDO and water via atomistic simulations. Density functional theory calculations are applied to identify various forms of sPBI structures and quantify their binding interactions with 2,3-BDO and water. Classical molecular dynamic simulations are used to evaluate the structural changes, diffusivity, and selectivity of 2,3-BDO and water in different sPBI models, GO surfaces, and GO-doped sPBI composite models. Our results suggest that sPBI slightly increases the crystallinity of the membrane structures, enhances the adsorption strength for both 2,3-BDO and water, and improves the water/2,3-BDO selectivity by 2–3 times. The GO surfaces display a maximum selectivity at a surface coverage of 0.1–0.15 for both hydroxyl and epoxy surface groups. The addition of GO flakes to sPBI creates new interaction sites for 2,3-BDO and water at the interface of sPBI and GO, and the water/2,3-BDO selectivity of GO-doped sPBI models is further increased up to 3 times. This work illustrates how the integrated addition of sPBI and GO flakes offers a promising approach to selective separation of 2,3-BDO and water, providing theoretical guidance for polybenzimidazole-based membranes in the potential application of 2,3-BDO recovery.

2,3-butanediol↗

DOE OSTI2022

Unexpected features in the optical vibrational spectra of δ-UO 3

Uranium trioxide displays a complex chemical phase space, with at least six structurally distinct polymorphs accessible via different synthetic routes. Remarkably, despite its technological importance, full structural and electronic characterization of these polymorphs remains an open area of study. δ-UO 3 in particular has attracted significant theoretical attention due to its high point group and space group symmetries, having U (VI) in octahedral coordination with polyhedra interconnected through corner-sharing to build a 3-D cubic lattice with space group symmetry Pm-3m and Z = 1. Critical experimental information, such as its optical vibrational spectra, are not known. Here, we study the Raman and infrared (IR) spectra of δ-UO 3 together with the support of density functional theory (DFT) calculations for spectral interpretation. A symmetry analysis of the DFT-predicted phonon eigenmodes indicates that δ-UO 3 should have two IR active modes and no Raman active modes. Experimental results, however, indicate significant Raman scattering from δ-UO 3 . We therefore propose four potential explanations for this apparent contradiction: a possible tetragonal distortion to the cubic cell, the existence of a surface impurity layer, vacancy scattering, and structural activation of Raman signal. We use powder X-ray diffraction and confocal Raman spectroscopy with depth profiling to investigate these possibilities and suggest future experiments to explore this phenomenon in more detail. Understanding the lattice dynamics of δ-UO 3 is important for identification of technogenic U phases via Raman and infrared spectroscopy and our results indicate that the simple understanding of δ-UO 3 as a high-symmetry cubic structure should be reconsidered.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

NASA NTRS1987

A preliminary study of Mars rover/sample return missions

The Solar System Exploration Committee (SSEC) of the NASA Advisory Council recommends that a Mars Sample Return mission be undertaken before the year 2000. Comprehensive studies of a Mars Sample Return mission have been ongoing since 1984. The initial focus of these studies was an integrated mission concept with the surface rover and sample return vehicle elements delivered to Mars on a single launch and landed together. This approach, to be carried out as a unilateral U.S. initiative, is still a high priority goal in an Augmented Program of exploration, as the SSEC recommendation clearly states. With this background of a well-understood mission concept, NASA decided to focus its 1986 study effort on a potential opportunity not previously examined; namely, a Mars Rover/Sample Return (MRSR) mission which would involve a significant aspect of international cooperation. As envisioned, responsibility for the various mission operations and hardware elements would be divided in a logical manner with clearly defined and acceptable interfaces. The U.S. and its international partner would carry out separately launched but coordinated missions with the overall goal of accomplishing in situ science and returning several kilograms of surface samples from Mars. Important considerations for implementation of such a plan are minimum technology transfer, maximum sharing of scientific results, and independent credibility of each mission role. Under the guidance and oversight of a Mars Exploration Strategy Advisory Group organized by NASA, a study team was formed in the fall of 1986 to develop a preliminary definition of a flight-separable, cooperative mission. The selected concept assumes that the U.S. would undertake the rover mission with its sample collection operations and our international partner would return the samples to Earth. Although the inverse of these roles is also possible, this study report focuses on the rover functions of MRSR because rover operations have not been studied in as much detail as the sample return functions of the mission.

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