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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Quantitative Determination of Electronic Effects in Free Radicals through Open-Shell Hammett Substituent Constants

Hammett substituent constants (σ), which quantify the electronic effects of functional groups, are widely used for predicting the properties of organic compounds and investigating reaction mechanisms. While these values have been obtained for a wide range of closed-shell substituents, measurements of analogous values for open-shell substituents are rare due to challenges associated with their short lifetimes. Here, in this report, we developed a combined experimental and computational approach for quantifying the electronic properties of open-shell substituents based on changes in nitrile vibrational frequencies (ν(C≡N)). By coupling pulse radiolysis and time-resolved infrared spectroscopy (PR-TRIR), we measured ν(C≡N) IR bands of 30 para - and meta -substituted benzonitriles bearing C-, N-, and S-centered radicals. A linear scaling relationship was obtained between these experimental values and values obtained from DFT calculations. Using these computed values, two different Hammett constants, σ m , and σ p + , were determined for a series of C-, N-, O-, S-, Si-, and B-centered radicals. The differences between σm and σp+ values enable the separate evaluation of inductive and resonance effects in these open-shell substituents. The results suggest that there are three classes of radicals: one is electron withdrawing (σ m , σ p + > 0), one is electron donating (σm, σp+ < 0), and one is inductively withdrawing but resonance donating (σ m > 0, σ p + < 0). Our study represents a general approach to the analysis of the electronic properties of open-shell species and has potential applications in a wide range of molecular processes involving free radical intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Stable Cycling of Mg Metal Anodes by Regulating the Reactivity of Mg 2+ Solvation Species

Rationally designing stable nonaqueous electrolytes for Mg metal anodes demands a thorough understanding of their interfacial behaviors. Here, the critical role of cation–anion pairing in improving the cathodic stabilities of amine-based electrolytes against solvent reduction and H 2 evolution is identified. It is demonstrated that strong coordination between solvating amine groups and the Mg 2+ cation facilitates the dehydrogenation of the -NH 2 group, which is mainly responsible for low reversibility during Mg metal plating and stripping. Introducing ion-pairing into the primary solvation shell can effectively weaken the amine coordination such that its reduction is suppressed. A novel interfacial behavior regarding parasitic reaction product dissolution is also identified, which is responsible for the failure of interfacial passivation. An ion-pairing electrolyte is developed based on a weakly-solvated amine molecule and strongly coordinating Mg 2+ salt. This electrolyte composition delivers long-term Mg metal anode cycling with 99.6% Coulombic efficiency for 800 cycles.

25 ENERGY STORAGE↗
DOE OSTI2022

Level density within a micro-macroscopic approach

Statistical level density $ρ$($E, A$) is derived for nucleonic system with a given energy $E$, particle number $A$ and other integrals of motion in the micro-macroscopic approximation beyond the standard saddle-point method of the Fermi gas model. This level density reaches the two limits; the well-known Fermi gas grand-canonical ensemble limit for a large entropy $S$ related to large excitation energies, and the finite micro-canonical limit for a small combinatorical entropy $S$ at low excitation energies. In conclusion, the inverse level density parameter $K$ as function of the particle number $A$ in the semiclassical periodic orbit theory, taking into account the extended Thomas-Fermi and Strutinsky shell corrections, is calculated and compared with experimental data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

In-line measurements of below-the-surface food deformation during drying with an interference-based optical fiber strain sensor

Real-time measurements of food deformation are important for quality control in drying, yet they pose significant challenges. In this study, we developed an interference-based optical fiber strain sensor to enable in-line, continuous, below-the-surface strain measurements in drying of soft food samples. Compared to a strain resolution of 8 × 10 -4 at zero strain and 7.2 × 10 -3 at 0.20 strain reported in our previously published work, the present study achieves markedly improved resolutions of 1.3 × 10 -4 at zero strain and 7.8 × 10 -4 at 0.25 strain, which strains are the lower and higher boundaries of the dynamic range, respectively. This nearly order-of-magnitude improvement is attributed to the unique interference-based sensing mechanism, no need for calibration to convert optical signals to strain, and the system-design-enabled immunity to fiber-disk misalignments and light source intensity fluctuations. To demonstrate the in-line process monitoring, deformation measurements of fresh banana slices and sugar cookie doughs were carried out in a benchtop oven and an industrial-scale hot-air pilot dryer, respectively. In both dryers, strain measurements were continuously measured during the whole drying process at various depths and radii below the sample surfaces, with the strains up to 25%. Computer vision was used only in the benchtop drying to confirm the faithfulness of the fiber sensor measurements and cannot provide below-the-surface measurements. The measured spatiotemporal deformation allowed us to confirm the shell-hardening effect and to determine the speed and location of large deformation changes in the whole drying process, the latter of which is related to the sample cracking. To the best of the authors’ knowledge, this study is the first to report on an interferometry-based fiber sensor to measure food deformation. This sensor and the sensing mechanism have high potential for real-time process monitoring and control to prevent over-drying or cracking during drying processes.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Dynamics of Materials at Extreme Pressure

The original proposal defined two classes of work: (1) shock dynamics in materials at the MEC endsta9on at LCLS x-ray laser at SLAC, and (2) study of the effect of shell structure and ioniza9on on the equa9on of state of carbon up to 1 Gbar at the NIF laser at LLNL. Support was requested for a graduate student and postdoc. This work, plus addi9onal science in related areas, was accomplished. The effort was funded 9/15/17 – 9/14/22 (through a no-cost extension).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Neutrinoless Double-Beta Decay Investigations of 82Se Using Three Shell Model Hamiltonians

Neutrinoless double-beta decay is considered one of the most promising processes that would help clarify some of the symmetry-breaking problems in our understanding of the observable universe. Recent studies of neutrinoless double-beta decay matrix elements have employed statistical approaches based on modified shell model effective Hamiltonians for 48Ca (Phys. Rev. C 106, 054302 (2022)) and 136Xe (Phys. Rev. C 107, 045501 (2023)). The analyses rely on inducing perturbations in the starting effective Hamiltonians to observe the behavior of a wide range of observables, besides the 0νββ) NME, that are compared with experimental data. Following a Bayesian model averaging approach, the range of probable values for the neutrinoless double-beta decay matrix elements is presented. In this paper, we present a similar study for 82Se, which is described in the same model space as 76Ge that is under experimental observation. Due to its faster calculation time compared to 76Ge, 82Se can be used as an appropriate substitute in our complex statistical study. Using the calculations performed for the statistical analysis of the neutrinoless double-beta decay matrix elements, we also search for the correlations between the observables that we can compare to experimental data.

Science & Technology - Other Topics↗
DOE OSTI2024

Improved Statistical Analysis for the Neutrinoless Double-Beta Decay Matrix Element of 136Xe

Neutrinoless double beta decay nuclear matrix element (M0ν) for 136Xe was recently analyzed using a statistical approach (Phys. Rev. C 107, 045501 (2023)). In the analysis, three initial shell model effective Hamiltonians were randomly altered, and their results for 23 measured observables were used to infer credibility for the M0ν nuclear matrix element (NME) based on a Bayesian Model Averaging approach. In that analysis, a reasonable Gamow-Teller quenching factor of 0.7 was assumed for each starting effective Hamiltonian. Given that the result of the statistical analysis was sensible to this choice, we are here improving that analysis by assuming that the Gamow-Teller quenching factor is also randomly chosen within reasonabe limits for all three starting Hamiltonians. The outcomes are slightly higher expectation values and uncertainties for the M0ν NME.

Astronomy & Astrophysics↗
DOE OSTI2023

Effect of a redox-mediating ligand shell on photocatalysis by CdS quantum dots

Semiconductor quantum dots (QDs) are efficient organic photoredox catalysts due to their high extinction coefficients and easily tunable band edge potentials. Despite the majority of the surface being covered by ligands, our understanding of the effect of the ligand shell on organic photocatalysis is limited to steric effects. We hypothesize that we can increase the activity of QD photocatalysts by designing a ligand shell with targeted electronic properties, namely, redox-mediating ligands. Herein, we functionalize our QDs with hole-mediating ferrocene (Fc) derivative ligands and perform a reaction where the slow step is hole transfer from QD to substrate. Surprisingly, we find that a hole-shuttling Fc inhibits catalysis, but confers much greater stability to the catalyst by preventing a build-up of destructive holes. We also find that dynamically bound Fc ligands can promote catalysis by surface exchange and creation of a more permeable ligand shell. Finally, we find that trapping the electron on a ligand dramatically increases the rate of reaction. Furthermore, these results have major implications for understanding the rate-limiting processes for charge transfer from QDs and the role of the ligand shell in modulating it.

Chemistry↗
DOE OSTI2025

Universal Effective Charges in the 𝑠⁢𝑑 and 𝑓⁡𝑝 Shells

The 247-keV state in 54 Sc, populated in the 𝛽 decay of 54 Ca, is reported here as a nanosecond isomer with a half-life of 26.0(22) ns. The state is interpreted as the 1 + member of the 𝜋⁢𝑓 7/2 ⊗ 𝜈⁢𝑓 5/2 spin-coupled multiplet, which decays to the 3 + ,𝜋⁢𝑓 7/2 ⊗ 𝜈⁢𝑝 1/2 ground state. The new half-life corresponds to a pure 𝐸⁢2 transition with a strength of 1.93(16) W.u., providing the most precise, unambiguous 𝐵⁡(𝐸⁢2) value in the neutron-rich 𝑓⁡𝑝 region to date for a nucleus with valence protons above 𝑍 = 20. Notably, it is roughly 4 times larger than the 𝐵⁡(𝐸⁢2;1/2 − → 5/2 − ) value in 55 Ca. The results, as compared to semiempirical and ab initio shell-model calculations, indicate (1) a weak 𝑁 = 34 subshell gap relative to 𝑁 = 32, (2) a large 𝐸⁢2 enhancement in Sc as compared to Ca due to 1⁢𝑝 − 1⁢ℎ proton excitations across 𝑍 = 28, and (3) empirical effective proton and neutron charges 𝑒 𝜋 = 1.30⁢(8)⁢𝑒 and 𝑒 𝜈 = 0.452⁢(7)⁢𝑒, respectively, that are in contrast to reports of 𝑒 𝜋 ≈1.1–1.15⁢𝑒 and 𝑒 𝜈 ≈ 0.6–0.8⁢𝑒 for 𝑓⁡𝑝-shell nuclei near 𝑁 = 𝑍. Here, we demonstrate that these reports are erroneous and that, in fact, a universal set of effective charges can be used across the 𝑠⁢𝑑 and 𝑓⁡𝑝 shells.

Beta decay↗
DOE OSTI2024

Characterizing the effects of drive asymmetries, component offsets, and joint gaps in double shell capsule implosions

This work provides a numerical study of how double shell capsule deformations caused by drive asymmetries and fabrication imperfections affect implosion symmetry and neutron yield. Hydrodynamics simulations are performed in two dimensions and focus on low-mode deformations that are caused by corresponding asymmetries in the Hohlraum drive, component offsets, and ablator joint gaps. By providing a parameter study of these features, our goal is to understand the dominant sources for inner shell deformation and yield degradation. The discussed capsules are composed of an aluminum ablator with a chromium inner shell. The latter encloses a carbon-deuterium foam ball that serves as fuel. We find that for clean capsules, even-numbered low-mode asymmetries in the drive are imprinted on the ablator and smoothly transferred to the inner shell during shell collision. The resulting deformation of the inner shell is more pronounced with larger fuel radius, while the yield is inversely proportional to the amplitude of the drive asymmetry and varies by factors ≤4 in comparison with clean simulations. Capsule component offsets in the vertical direction and ablator thickness nonuniformity result in p1-type deformations of the imploding inner shell. Finally, joint gaps have the largest effect in deforming the ablator and inner shell and degrading yield. While small gap widths (1 μm) result in prolate inner shells, larger gap widths (4 μm) cause an oblate deformation. More importantly, capsules with a small outer gap (1 μm) experience a dramatic drop in yield, typically <3% of a clean simulation.

Goodarzi, S. (ORCID:000000018556489X)↗
DOE OSTI2025

𝐷-shell mixing in light baryons and its effect on the orbital motion

The standard description of the nucleon in the nonrelativistic quark model is an 1S,L = 0 state without orbital motion. Yet, there are several indications from phenomenology that an admixture of states with nonzero orbital motion maybe substantial. In this paper we focus on the “second shell” of the nucleon excitations (D-shell), for which we give a modern description of the wave functions. We follow it by investigating what we call a “maximal mixing” scenario, assuming a hypothetical long-range tensor force. We give the explicit wave functions for all states, before and after mixing, and reassess many predictions such as the magnetic moments, the standard and transitional form-factors from the nucleon to N*. Unexpectedly, in this scenario we can reproduce the long-puzzling features of the Roper resonance N*(1440). But even in this extreme case, the admixture of the 1D,L = 2 state to a nucleon remains significantly smaller than expected from phenomenology.

Baryons↗
DOE OSTI2025

Impact of Ligands on the Ion–Ion Selectivity of Ligand-Appended-Pillar[ n ]arene Channels

Ligand-appended pillar[5]arene (LAP) channels are emerging as a promising platform for ion-selective membranes. In this study, we investigated the ion selectivities of three LAP channels functionalized with distinct ligands: diglycolamine, carbamoylmethyl phosphine oxide, and propionamide phosphonic acid. These ligands were chosen based on their demonstrated affinities for lanthanides in solvent extraction studies. We examined the selectivity of each channel toward a series of monovalent, divalent, and trivalent ions: Li + , Na + , K + , Mg 2+ , Ca 2+ , La 3+ , Eu 3+ , and Yb 3+ . To quantify ion-channel interactions and the energetics of translocation, we computed the potential of mean force (PMF) profiles for each ion. These PMFs were subsequently recast into permeability coefficients, enabling a direct evaluation of ion permselectivity. Our results reveal distinct selectivity patterns governed by the chemical nature of the appended ligands. The diglycolamine-functionalized channel exhibits strong interactions with monovalent ions, leading to replication of the Li + bulk hydration shell within the channel. This promotes preferential transport Li + ions while effectively excluding divalent and trivalent species. In contrast, the carbamoylmethyl phosphine oxide-functionalized channel displays a reduced selectivity between monovalent ions while similarly exhibiting an effective rejection of divalent and trivalent ions. This arises from steric hindrance around channel-lining oxygens imposed by the ligand's bulky phenyl groups which limits heavy ion coordination and promotes retention of hydration shells effectively increasing effective ion size. The propionamide phosphonic acid-functionalized channel exhibits a different trend, favoring ions with lower hydration free energies, with K + ions showing enhanced permeation. These findings highlight the critical role of ligand-ion interactions in modulating ion selectivity within LAP channels. In particular, the strong coordination exhibited by diglycolamine and propionamide phosphonic acid ligands significantly influences the ion transport energetics and selectivity profiles.

hydration↗
DOE OSTI2023

Probing proton cross-shell excitations through the two-neutron removal from 38 Ca

Bound states of the neutron-deficient, near-dripline nucleus 36 Ca were populated in two-neutron removal from the ground state of 38 Ca, a direct reaction sensitive to the single-particle configurations and couplings of the removed neutrons in the projectile wave function. Final-state exclusive cross sections for the formation of 36 Ca and the corresponding longitudinal momentum distributions, both determined through the combination of particle and γ-ray spectroscopy, are compared to predictions combining eikonal reaction theory and shell-model two-nucleon amplitudes from the USDB, USDC, and ZBM2 effective interactions. The final-state cross-section ratio σ($2$$^{+}_{1}$) / σ (0 + ) shows particular sensitivity and is approximately reproduced only with the two-nucleon amplitudes from the ZBM2 effective interaction that includes proton cross-shell excitations into the pf shell. Characterizing the proton pf-shell occupancy locally and schematically, an increase of the sd – pf shell gap by 250 keV yields an improved description of this cross-section ratio and simultaneously enables a reproduction of the B(E2;$0$$^{+}_{1}$ → $2$$^{+}_{1}$) excitation strength of 36 Ca. Furthermore, this highlights an important aspect if a new shell-model effective interaction for the region was to be developed on the quest to model the neutron-deficient Ca isotopes and surrounding nuclei whose structure is impacted by proton cross-shell excitations.

20 ≤ A ≤ 38↗
DOE OSTI2024

Abstract for CRADA between National Energy Technology Laboratory and Shell International Exploration & Production, Inc

Introducing CO₂ into geothermal systems as a working fluid in reservoirs can enhance geothermal conductivity, production, and pressure maintenance. A cross-disciplinary interaction of geothermal reservoir stimulation and CO₂ utilization satisfies renewable energy demands and operations that support sustainable energy infrastructure. Challenges to implementing CO₂-stimulated geothermal enhancement (CS-GE) include (1) accurately characterizing and imaging CO₂-stimulated geothermal reservoirs; (2) quantitatively inferring CS-GE evolution under current and future engineered conditions for cost effective operations; and (3) monitoring resources by improving observational methods to advance the understanding of complex geothermal systems for sweep efficiency and, ultimately, cost effectiveness. NETL and Shell will collaborate under this CRADA to develop software to image key features, including CO₂-stimulated fracture imaging, CO₂ fluid sweep imaging and heat transfer and exchange imaging by leveraging available datasets and applying advanced Artificial Intelligence/Machine Learning (AI/ML), multi-level data analytics and data/information fusion to better understand the comprehensive mechanisms of CO₂-stimulated geothermal systems.

15 GEOTHERMAL ENERGY↗
DOE OSTI2023

Energy variation of double K -shell photoionization of Ne

Herein we report on an experimental and theoretical study of double K-shell photoionization of Ne over the 2.3–8.5 keV x-ray energy range. The ratio of double-to-single K-shell photoionization cross sections was determined experimentally by measuring the relative rates of the KK–KL 2,3 L 2,3 ( 2 D) Auger hypersatellite and the K–L 2,3 L 2,3 ( 1 D) diagram Auger transitions. By scaling the hypersatellite-diagram Auger-electron ratios to KK/K cross-section ratios, comparison was made with theoretical cross-section ratios of He-like Ne 8+ determined by the R matrix with pseudostates method. The experimental Ne and theoretical Ne 8+ cross-section ratios show similar variations with energy, but the experimental ratios systematically exceed the calculated ratios and also show a lower threshold energy for double K-shell photoionization onset compared to the computed Ne 8+ threshold. The discrepancy is attributed to effects of L-shell electrons not included in the He-like Ne 8+ calculations. Quantified scaling with nuclear charge Z along the He-like isoelectronic sequence indicates that the measured 10-electron Z = 10 double K-shell photoionization cross section behaves like the computed He-like Z = 8.9 cross section, suggesting an effective nuclear screening parameter of s L =1.1 by the additional eight outer L-shell electrons. Experimental results for the energy variations of Auger electron transitions from other multielectron hole states are also discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Quantifying Size Effects on Thermal Transport in CsPbBr 3 Nanocrystal Films

Colloidal lead halide perovskite nanocrystals (LHP NCs) are promising semiconductor materials for optoelectronic applications due to their strong quantum confinement, near-unity photoluminescence quantum yields, and tunable emission characteristics. However, their modest thermal stability remains a challenge, particularly at smaller core diameters due to enhanced phonon scattering at inorganic core-organic ligand interfaces. In this work, we directly quantify size-dependent thermal conductivity (κ) in lecithin-capped CsPbBr 3 NC thin films using a transducer-free, vibrational pump–visible probe (VPVP) spectroscopy technique. A mid-infrared pump thermally excites the ligand shell, while a broadband probe tracks transient reflectance change correlated to lattice temperature decay. Finite-element modeling of the decay dynamics yields κ values from 0.13 to 0.16 W·m –1 ·K –1 for NC films with sub-10 nm core diameter, significantly lower than those of its bulk counterpart. A steep κ suppression with decreasing NC size emphasizes the dominant role of ligand shells and boundary effects in thermal transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗