Search NASA⌕ Search

SEARCH · Search NASA

Results for “decadal study”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

A New Theoretical Framework for Designing Ion Transport Pathways

The rapid transport of specific ions through matter is critical to energy storage, membrane separations, and health. However, commercial materials resist ion transport, lack specificity, or both, making ion transport costly and ineffective. Inspiration for new material designs can be taken from biology, where membrane transport proteins exert exquisite control over the specificity and rate of ion transport. The challenge in understanding and designing transport pathways is that ions often exchange their hydrating waters for direct contacts with atoms in the transport pathway. Despite intense study over decades, no theory exists to explain local ion binding and transport mechanisms and experiments cannot differentiate reliably between ions and water in binding sites. Here, we developed a new approach, based on quantum methods and extension of the quasi-chemical free energy theory, to understand and design pathways through materials for rapid transport of specific ions. Understanding ion transport mechanisms will significantly advance our nation’s ability to develop cost-effective materials for energy sustainability and therapeutics for health.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Quantum Choreography of the Nucleus: Rotations, Vibrations, and Emergent Structure

Abstract Nuclei are complex many-body quantum systems where interactions of the neutrons and protons via the strong, the weak, and the electromagnetic forces lead to the emergence of simple patterns of energy states that have been described by various theoretical approaches. One of the goals of all the theoretical models is the development of a universal theory that can be applied across the entire chart of nuclides. Significant progress has been made by experiments as well as the increasing sophistication of models, but a universal theory has yet to be established. A recent review of nuclei in the Z = 50–82 region of the chart of nuclides has analyzed all the available compiled data from several decades of studies towards a clarification of the low-lying structure of nuclei. Other reviews have reported and explained the emergence of multiple different shapes in nuclei at somewhat higher excitation energies than the ground state. Some have challenged the interpretation of the first excited K π = 0 + band as a vibration of ground state. This work attempts to provide a guide to determining the nature of the first excited K π = 0 + band in nuclei by the combined use of nuclear lifetimes, energy level evolutions, dynamic moments of inertia, and intrinsic quadrupole moments extracted from transition probabilities. The result is that for a subset of the nuclei in this region, the K π = 0 + band is consistent with the traditional 𝛽-vibration description of an oscillation built on the ground state.

CHFB+5DCH↗
DOE OSTI2026

Stability and Characteristics of Lower-hybrid Drift Waves: Dependence on Electron Beta and Cross-field Relative Drift

Lower-hybrid drift waves (LHDWs) are frequently observed microinstabilities in both space and laboratory plasmas. Despite decades of study, the relationship between electrostatic (ES-LHDW) and electromagnetic (EM-LHDW) variants and the plasma parameters controlling their stability remains unclear. Here, we systematically examine LHDW behavior by solving the local linear dispersion relation over a wide range of plasma and field conditions. Our results demonstrate that ES-LHDWs and EM-LHDWs are not distinct modes but rather two different regimes of the same drift wave whose character evolves smoothly with electron beta (β e ) and the cross-field electron drift velocity relative to ions, normalized to the ion sound speed (u 0x /C s ). The nature of the waves changes from electrostatic to electromagnetic when β e increases. Growth rates increase with u 0x /C s but decrease with β e , while the most unstable wavelength remains nearly universal, with kρ e ∼ 0.8 (k is the magnitude of the wave vector and ρ e is the electron gyroradius). We further present quasi-linear estimates of nonlinear saturation properties, including energy partition among electric fields, magnetic fields, and particle kinetic responses. We show that ES-LHDWs reach higher electric-field saturation amplitudes, whereas EM-LHDWs generate strong magnetic perturbations and parallel electric fields that may enable efficient particle heating. Comparisons with the classical model reveal that retaining electromagnetic effects is essential for accurate predictions of frequency, growth rate, and the propagation angle. These findings provide a unified framework for understanding LHDWs across diverse collisionless plasma environments, including current sheets of magnetic reconnection, shear layers, collisionless shocks, and boundary regions.

Solar coronal waves↗
DOE OSTI2024

Measurement of the Neutron Electromagnetic Form Factor Ratio at High Momentum Transfer

The inner structure of the nucleon (proton and neutron) remains a topic of great interest in nuclear and particle physics, after many decades of study. For example, understanding the quark-gluon dynamics inside the nucleon would shed light on how 99% of the nucleon mass is created. The neutron electromagnetic form factors, Gn E and Gn M , give important insights into the neutron structure. The Super BigBite Spectrometer (SBS) program at Jefferson Lab (JLab) seeks to extend the form factor measurements for both the proton and the neutron. The neutron electric form actor, Gn E , has been historically difficult to measure due to the short lifetime of the free neutron and the small value of Gn E . The GEn-II experiment is part of the SBS program and seeks to measure Gn E , significantly increasing the high momentum transfer coverage. A newly designed polarized 3He target increased the figure of merit by three times compared to previous measurements. The analysis of this data is especially challenging due to the unprecedented high-rate environment caused by the open nature of the spectrometer with a direct line of sight to the target. This required developing new Gas Electron Multiplier (GEM) particle trackers which can cover large areas demanded by this setup and handle particle rates up to 500 kHz/cm2. Rates this high over a large area is unprecedented in particle tracking systems and came with a number of challenges. Data taken in the SBS program was critical to understanding hardware and software solutions that improved the track reconstruction efficiency to be >97% with a position resolution of 70 ?m. In previous experiments the proton electromagnetic form factors, Gp E and Gp M were measured up to Q2 = 8.5 GeV2 and Q2 = 30 GeV2, respectively, while Gn E has only been measured up to Q2 = 3.4 GeV2. The GEn-II experiment has measured the neutron form factor ratio, Gn E/Gn M, at Q2 values of 2.90, 6.50, and 9.47 GeV2 by scattering a polarized electron beam with a polarized 3He target, used here as an effective polarized neutron target, and measuring the double spin asymmetry of the cross section. Previous Gn E measurements do not extend above Q2 = 3.4 GeV2, and therefore this analysis has extended the world data by almost three times. The background correction is especially difficult at the higher Q2 settings leading to large systematic errors. As very exploratory results from this early analysis of the data, we find for Q2 = 2.90 GeV2, Gn E = 0.0157 ±stat 0.0016 ±sys 0.0011, for Q2 = 6.50 GeV2, Gn E = 0.0067 ±stat 0.0019 ±sys 0.0005, and for Q2 = 9.46 GeV2, Gn E = 0.0046 ±stat 0.0023 ±sys 0.0005. These results are compared to predictions from the Dyson-Schwinger Equations (DSE) model and a Relativistic Constituent Quark Model (RCQM).

Jeffas, Sean↗
DOE OSTI2025

Arctic sea-ice loss drives a strong regional atmospheric response over the North Pacific and North Atlantic on decadal scales

Previous studies have suggested that Arctic sea-ice loss can have a profound influence on atmospheric circulation far away from the Arctic. However, there is little scientific consensus on the features of these remote responses, with the opposite impacts reported. Here we present a multi-model analysis of the decadal climate response to Arctic sea-ice loss using state-of-the-art energy conserving methodologies to isolate the impacts of sea-ice decline. We observe weakening of the Aleutian Low and development of a geopotential ridge in the North Pacific, associated with drier winter conditions over the southwest United States. Over the Atlantic, a negative NAO-like response drives wetter winter conditions across the western Mediterranean. These decadal-scale impacts substantially differ from reported centennial-scale responses to Arctic sea-ice loss simulated using non-energy conserving methodologies. Factors such as the timescale of the response and methodologies used to isolate the impacts of disappearing sea-ice cover should be carefully considered when consolidating scientific understanding on the future impacts of changing Arctic.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

A detailed chemical study of the extreme velocity stars in the galaxy

ABSTRACT Two decades on, the study of hypervelocity stars is still in its infancy. These stars can provide novel constraints on the total mass of the Galaxy and its dark matter distribution. However how these stars are accelerated to such high velocities is unclear. Various proposed production mechanisms for these stars can be distinguished using chemo-dynamic tagging. The advent of Gaia and other large surveys have provided hundreds of candidate hyper velocity objects to target for ground-based high-resolution follow-up observations. We conduct high-resolution spectroscopic follow-up observations of 16 candidate late-type hyper velocity stars using the Apache Point Observatory and the McDonald Observatory. We derive atmospheric parameters and chemical abundances for these stars. We measure up to 22 elements, including the following nucleosynthetic families: $\alpha$ (Mg, Si, Ca, and Ti), light/odd-Z (Na, Al, V, Cu, and Sc), Fe-peak (Fe, Cr, Mn, Co, Ni, and Zn), and neutron capture (Sr, Y, Zr, Ba, La, Nd, and Eu). Our kinematic analysis shows one candidate is unbound, two are marginally bound, and the remainder are bound to the Galaxy. Finally, for the three unbound or marginally bound stars, we perform orbit integration to locate possible globular cluster or dwarf galaxy progenitors. We do not find any likely candidate systems for these stars and conclude that the unbound stars are likely from the the stellar halo, in agreement with the chemical results. The remaining bound stars are all chemically consistent with the stellar halo as well.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

A decade of progress in understanding and managing legacy well integrity for geologic carbon storage

This study reviews a decade of research progress in legacy well integrity and risk management for geologic carbon storage (GCS) to commemorate the 20 th anniversary of the Intergovernmental Panel on Climate Change’s 2005 Special Report on Carbon Capture and Storage. In the past ten years, legacy well research has benefited from global efforts to constrain emissions from abandoned oil and gas wells, a continued focus on well materials performance in the presence of CO 2 -rich fluids, and practical experience gained through GCS implementation. Field measurements of abandoned well emissions show that leakage is not universal or catastrophic but forms a continuum of low-to-moderate fluxes that depend on isolation integrity and environmental attenuation. Materials research has constrained the conditions under which Portland cements exhibit self-sealing and non-sealing behaviors, and has identified the impact of geomechanical properties, non-uniform pathway apertures, multi-phase flow, and impurities in the CO 2 stream, on leakage pathways as important new areas for investigation. GCS projects at brownfield sites have inspired the creation of new workflows that integrate various tools and technologies to manage legacy well leakage risks. GCS implementation has also motivated a push towards scenario-based well modeling that directly informs permit applications. These advances inspire new research questions for the coming decade, particularly around the level of legacy well leakage risk that is environmentally acceptable and tolerable to stakeholders when sequestering millions of tonnes of CO 2 annually.

Carbon capture and storage↗
DOE OSTI2025

Nonpigmented PsbR is involved in the integrity of excitation landscape in higher plant photosystem II, a case study in Arabidopsis thaliana and a mutant

PsbR is a nonpigmented 10 kDa protein in Photosystem II (PSII) in algae and plants. A recent structural study clarified its enigmatic structural location in a Photosystem II megacomplex that has baffled the community for more than four decades. Our current study interrogates whether absence of PsbR affects the overall dynamics of excitation energy migration within light harvesting complexes (LHC) and PSII super assemblies using highly-active PSII membrane particles, so-called BBY particles, isolated from a PsbR deletion mutant (ΔPsbR) of Arabidopsis thaliana. A femto-second (fs)-time-resolved transient absorption experimentation recorded at 77 K with selective excitation of Chl b which is exclusively present in LHCs enabled us to resolve the temporal differences in LHC→LHC and LHC→PSII excitation energy transfer steps. By applying specific target spectro-kinetic models to the transient absorption datasets, we demonstrated that the time constants of Chl a LHC → Chl a LHC excitation transfer significantly elongates in the ΔPsbR LHC-PSII particles, suggestive of the decreased aggregation level of photosynthetic proteins in the mutant. These findings highlight excitation energy transfer integrity in LHC-PSII assembly is not only determined by the pigmented light-harvesting complexes, but also synergistically by the nonpigmented PSII components. Furthermore, the disturbed integrity in dynamics of excitation energy transfer pathway within LHC-PSII supercomplex is discussed in the context of the altered LHC-PSII megacomplexes type I and II architectures which result from the absence of the PsbR protein in higher plant PSII.

Chlorophyll↗
DOE OSTI2025

Pressure Variation of Magnetism in Chromium and Manganese Mono-Pnictide Superconductors

The transition-metal pnictide system MX (M = transition metal and X = P, As, and Sb) has been studied for several decades because those materials show rich magnetic phase diagrams. Since the recent discovery of unconventional superconductivity in isomorphic CrAs and MnP under high pressures, physical properties of the two materials have been investigated intensively as a function of pressure. In particular, since both materials exhibit quantum critical behavior with applied pressure, magnetic fluctuations are considered to be the key to the superconducting pairing mechanism. Interestingly, both materials were found to show double helical spin structures in the vicinity of the pressure-induced superconducting phase. Here, a review is given on the magnetic properties of MX, including our high-pressure neutron scattering studies performed in CrAs and MnP. We also give a brief review on technical developments of high pressure cells for neutron diffraction, including the high pressure cells used for our high pressure measurements in CrAs and MnP.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Deactivating Emission in Azulene via Solvent-Induced (Anti)Aromaticity

Anti-Kasha emission is a coveted feature in optoelectronics, with promise in areas such as imaging, sensing, and the production of white-light LEDs via dual-photon emission. Despite being a rare feature in organic systems, anti-Kasha emission is readily observed in the deceptively simple molecule azulene, which possesses two bright singlet states in the UV–visible spectrum and readily emits from the S 2 state. With dominant anti-Kasha emission and decades of synthetic study, azulene is a perfect candidate for novel material fabrication; however, large gaps persist in understanding the photophysics of even the simple parent compound. These range from competing, experimentally unverified models of azulene reactivity and aromaticity to the unexplained deactivation of anti-Kasha emission in a host of azulene derivatives. Herein, we use fluorescence and transient absorption spectroscopies to explore the detailed solvent dependence of azulene photophysics. We discover a tunable reduction in the S 2 lifetime via weak complexation with aromatic solvents. Interestingly, our results are independent of polarity, highlighting the primacy of peripherally delocalized 10-π Hückel aromaticity over zwitterionic character. When the dipolar character is enhanced through chemical functionalization, we observe even greater sensitivity to solvent aromaticity and more rapid quenching, revealing the role of conical intersections in azulenes with zwitterionic excited states. Overall, this work provides essential mechanistic insight into the photophysics of azulene and reveals a simple new approach to control the excited-state aromaticity and anti-Kasha emission in this class of materials.

Absorption↗
DOE OSTI2025

Rippled metamaterials with scale-dependent tailorable elasticity

Thermally induced ripples are intrinsic features of nanometer-thick films, atomically thin materials, and cell membranes, significantly affecting their elastic properties. Despite decades of theoretical studies on the mechanics of suspended thermalized sheets, controversy still exists over the impact of these ripples, with conflicting predictions about whether elasticity is scale-dependent or scale-independent. Experimental progress has been hindered so far by the inability to have a platform capable of fully isolating and characterizing the effects of ripples. This knowledge gap limits the fundamental understanding of thin materials and their practical applications. Here, we show that thermal-like static ripples shape thin films into a class of metamaterials with scale-dependent, customizable elasticity. Utilizing a scalable semiconductor manufacturing process, we engineered nanometer-thick films with precisely controlled frozen random ripples, resembling snapshots of thermally fluctuating membranes. Resonant frequency measurements of rippled cantilevers reveal that random ripples effectively renormalize and enhance the average bending rigidity and sample-to-sample variations in a scale-dependent manner, consistent with recent theoretical estimations. The predictive power of the theoretical model, combined with the scalability of the fabrication process, was further exploited to create kirigami architectures with tailored bending rigidity and mechanical metamaterials with delayed buckling instability.

Applied Physical Sciences↗
DOE OSTI2025

On the origins of the continuum radiation of an underwater nanosecond pulsed discharge: an absolute-intensity optical emission spectroscopy study

The plasma properties of an underwater nanosecond pulsed discharge remain not fully understood despite being extensively studied for several decades. In this work, we focus on the continuum radiation generated in such discharges. The discharge is characterized by power measurements as well as by absolute emission spectroscopy. When observed, Stark broadenings of H α , H β and O (777 nm) are employed for electron number densities measurements. The discharge was generated by a 10 ns main voltage pulse followed by multiple secondary pulses, which last up to 4 μs after the primary pulse. It is shown that a peak power of 3.5 MW and energy of 35 mJ is coupled during the main voltage pulse. A quantitative estimation of the different possible continuum radiation sources is performed through analytical calculations. This includes emission (blackbody, free–bound and free–free bremsstrahlung radiations) and absorption (electron–ion and electron–neutral free–free inverse bremsstrahlung) mechanisms. Our results suggest that electron–neutral free–free bremsstrahlung is the principal mechanism responsible for the strong continuum radiation observed experimentally during the primary pulse. We also show that self-absorption through electron–neutral (and electron–ion) inverse bremsstrahlung plays an important role in the main discharge pulse. Further, our results indicate the non-negligible additional contribution of the H 2 continuum during the first reflected pulse which is likely ignited in bubbles generated by the first discharge pulse.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Electronic glasses from a broken gauge symmetry in disorder-free systems

Glass phases can be stabilized by quenched disorders, as in most spin-glass materials, or self-generated through kinetic freezing in disorder-free systems. A canonical example of the latter is structural glasses, which have been extensively studied for many decades. Yet, how the rugged energy landscape of a glass phase is spontaneously generated in disorder-free systems remains one of the key questions in glass physics. Here, in this work, we present a general electronic mechanism for the emergence of glassy phase using the example of itinerant electrons coupled to XY spins on a lattice. This model can also be viewed as the mean-field theory of a superconducting system with attractive density-density interactions. Intriguingly, the electron gauge symmetry in the strong pairing limit gives rise to a macroscopic degeneracy of XY spins. In the presence of electron hopping that breaks the gauge symmetry, the lifting of the extensive degeneracy leads to a glass phase with disordered pairings. Our findings highlight a scenario in which a glassy state originates from the breaking of quantum gauge symmetry without quenched disorders.

XY model↗
DOE OSTI2024

Dynamically patterning x-ray beam by a femtosecond optical laser

Modern science and technology have greatly benefitted from our ability to precisely manipulate light waves, in both their spatial and temporal degrees of freedom. In the x-ray region, however, spatial control has been virtually static mainly due to stringent requirements for realizing high-performance optical elements. The lack of dynamic spatial control of x-ray beam has prevented researchers from realizing more sophisticated use of the wave field, which has rapidly advanced in the optical region in the past decades. In this study, we propose a practical scheme to dynamically control local x-ray reflectivity of a perfect silicon crystal by a femtosecond optical laser and demonstrate a programmable spatial x-ray modulator. Our modulator aims for spatial manipulation of the x-ray amplitude and is shown to produce arbitrary grayscale patterns with spatial frequencies up to 25 per millimeter. The proposed modulation scheme opens up a platform to enable advanced x-ray sensing and imaging techniques that can fully harness the wave nature of x-rays.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Probabilistic projections of the Amery Ice Shelf catchment, Antarctica, under conditions of high ice-shelf basal melt

Abstract. Antarctica's Lambert Glacier drains about one-sixth of the ice from the East Antarctic Ice Sheet and is considered stable due to the strong buttressing provided by the Amery Ice Shelf. While previous projections of the sea-level contribution from this sector of the ice sheet have predicted significant mass loss only with near-complete removal of the ice shelf, the ocean warming necessary for this was deemed unlikely. Recent climate projections through 2300 indicate that sufficient ocean warming is a distinct possibility after 2100. This work explores the impact of parametric uncertainty on projections of the response of the Lambert–Amery system (hereafter “the Amery sector”) to abrupt ocean warming through Bayesian calibration of a perturbed-parameter ice-sheet model ensemble. We address the computational cost of uncertainty quantification for ice-sheet model projections via statistical emulation, which employs surrogate models for fast and inexpensive parameter space exploration while retaining critical features of the high-fidelity simulations. To this end, we build Gaussian process (GP) emulators from simulations of the Amery sector at a medium resolution (4–20 km mesh) using the Model for Prediction Across Scales (MPAS)-Albany Land Ice (MALI) model. We consider six input parameters that control basal friction, ice stiffness, calving, and ice-shelf basal melting. From these, we generate 200 perturbed input parameter initializations using space filling Sobol sampling. For our end-to-end probabilistic modeling workflow, we first train emulators on the simulation ensemble and then calibrate the input parameters using observations of the mass balance, grounding line movement, and calving front movement with priors assigned via expert knowledge. Next, we use MALI to project a subset of simulations to 2300 using ocean and atmosphere forcings from a climate model for both low- and high-greenhouse-gas-emission scenarios. From these simulation outputs, we build multivariate emulators by combining GP regression with principal component dimension reduction to emulate multivariate sea-level contribution time series data from the MALI simulations. We then use these emulators to propagate uncertainty from model input parameters to predictions of glacier mass loss through 2300, demonstrating that the calibrated posterior distributions have both greater mass loss and reduced variance compared to the uncalibrated prior distributions. Parametric uncertainty is large enough through about 2130 that the two projections under different emission scenarios are indistinguishable from one another. However, after rapid ocean warming in the first half of the 22nd century, the projections become statistically distinct within decades. Overall, this study demonstrates an efficient Bayesian calibration and uncertainty propagation workflow for ice-sheet model projections and identifies the potential for large sea-level rise contributions from the Amery sector of the Antarctic Ice Sheet after 2100 under high-greenhouse-gas-emission scenarios.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

The National Climate Data Base (NCDB): A Bias-Corrected High-Resolution Climate Dataset

Assessing renewable energy resources under future climate scenarios has been highlighted in recent years to analyze and understand potential impacts of future change in renewable generation on the power sector. Solar energy is well-known as the most plentiful among various renewable resources and usually converted to electricity using photovoltaics (PV) technologies, and the global deployment of PV technology has increased rapidly in recent decades. In this study, we develop a statistical technique to downscale the future projection of solar irradiance for PV energy-related applications. A set of Regional Climate Model (RCM)-based projections obtained from the North American Coordinated Regional Climate Downscaling Experiment (NA-CORDEX) are used as inputs to statistical methods to generate high-resolution global horizontal irradiance (GHI) over the contiguous United States (CONUS). The main steps of the statistical downscaling method include (1) regridding RCM output (0.22 degree and daily resolutions) to handle the modeled-observed data sets on a common grid, (2) correcting bias of RCM GHI using satellite-derived observation, and (3) implementing temporal and spatial downscaling to generate GHI at 8-km and hourly resolution. Basically, complex physical processes and interactions between solar radiation and various atmospheric constituents lead solar irradiance to be highly variable and uncertain. Underrepresentation of clouds from the RCM parameterizations is the main source of error and uncertainty in modeling solar irradiance. Thus, we adapt and use the high-quality satellite-derived data from the National Solar Radiation Database (NSRDB) to analyze the bias and error of RCM GHI as well as estimate the statistical parameters for spatial and temporal downscaling. This presentation will summarize the comprehensive analysis conducted to produce and assess the results under two climate scenarios (RCP4.5 and RCP8.5). We will also present a detailed validation demonstrating the strengths of the proposed downscaling method and future extension of this research.

climate data↗
DOE OSTI2025

Perturbative treatment of nonlocal chiral interactions in auxiliary-field diffusion Monte Carlo calculations

Nuclear many-body systems, ranging from nuclei to neutron stars, are some of the most interesting physical phenomena in our universe, and quantum Monte Carlo (QMC) approaches are among the most accurate many-body methods currently available to study them. In recent decades, interactions derived from chiral effective field theory (EFT) have been widely adopted in the study of nuclear many-body systems. One drawback of the QMC approach is the requirement that the nuclear interactions need to be local, whereas chiral EFT interactions usually contain nonlocalities. In this work, we leverage the capability of computing second-order perturbative corrections to the ground-state energy in order to develop a self-consistent approach to including nonlocal operators in QMC calculations. In conclusion, we investigate both the deuteron and the neutron-matter equation of state in order to show the robustness of our technique and pave the way for future QMC calculations at higher orders in the EFT, where nonlocal operators cannot be avoided.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Thermodynamic insight into AnO 2 + bonding from ThH + /UH + reactions studied by inductively coupled plasma tandem mass spectrometry

The bonding mechanisms of actinides have been a focus of fundamental research over the past few decades. In the present study, reactions of the simplest actinide-containing species, ThH + and UH + , with O 2 and CO 2 are investigated by inductively coupled plasma tandem mass spectrometry. The reactions of ThH + and UH + with O 2 are efficient, and the reactions of ThH + and UH + with CO 2 display reduced reaction efficiencies. For both reactions involving CO 2 , ThO 2 + and UO 2 + are observed; however, there is a clear barrier to ThO 2 + formation whereas UO 2 + forms through an exothermic, barrierless process. The experimental observations and available thermodynamic information are used to predict the outcomes of reactions involving the later AnH + . The anticipated reaction enthalpies for Pa–Am display a clear correlation with the promotion energy of An + to a 6d 2 electronic configuration, E p (6d 2 ), although a shift in the slope of the correlation of reaction enthalpies and E p (6d 2 ) suggests that there is likely a change in bonding mechanism that starts with Np + . Similar shifts have also been noted in previous studies. Beginning with Np + , the 6d orbitals become less accessible than they are for the earlier An + as measured by E p (6d 2 ), and this accessibility of the 6d orbitals may drive actinide bonding.

5f orbitals↗