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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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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Heterogeneous isotope effects decouple conifer leaf and branch sugar δ 18 O and δ 13 C

Isotope ratios of tree-ring cellulose are a prominent tool to reconstruct paleoclimate and plant responses to environmental variation. Current models for cellulose isotope ratios assume a transfer of the environmental signals recorded in bulk leaf water to carbohydrates and ultimately into stem cellulose. However, the isotopic signal of carbohydrates exported from leaf to branch may deviate from mean leaf values if spatial heterogeneity in isotope ratios exists in the leaf. We tested whether the isotopic heterogeneity previously observed along the length of a ponderosa pine (Pinus ponderosa) leaf water was preserved in photosynthetic products. We observed an increase in both sugar and bulk tissue δ 18 O values along the needle, but the increase in carbohydrate δ 18 O values was dampened relative to the trend observed in leaf water. In contrast, δ 13 C values of both sugar and bulk organic matter were invariant along the needle. Additionally, phloem-exported sugar measured in the branch below the needles did not match whole-needle values of δ 18 O or δ 13 C. Instead, there was a near-constant offset observed between the branch and needle sugar δ 13 C values, while branch δ 18 O values were most similar to δ 18 O values observed for sugar at the base of the needle. The observed offset between the branch and needle sugar δ 18 O values likely arises from partial isotope oxygen exchange between sugars and water during phloem loading and transport. An improved understanding of the conditions producing differential δ 13 C and δ 18 O isotope effects between branch phloem and needle sugars could improve tree-ring-based climate reconstructions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Nuclear–Electronic Orbital General Rate Theory: Predicting Hydrogen Kinetic Isotope Effects in the Deep Tunneling Regime

Hydrogen transfer is a critical component of many chemical and biological processes. The ratio of rate constants for hydrogen and deuterium transfer defines the H/D kinetic isotope effect (KIE), which is a powerful tool for elucidating hydrogen transfer mechanisms. Interpretation of experimental H/D KIEs relies on accurate and affordable computational methods. However, due to their light mass, hydrogen and deuterium can undergo tunneling, which is challenging to describe in multidimensional molecular systems. Herein, we introduce the nuclear–electronic orbital general rate theory (NEO-GRT), which enables the efficient prediction of H/D KIEs based on full-dimensional molecular quantum chemistry calculations. The NEO-GRT approach describes the hydrogen transfer rate constant with a general expression that spans the vibrationally adiabatic and nonadiabatic hydrogen tunneling regimes. The input quantities are computed using NEO density functional theory, which treats the transferring hydrogen or deuterium nucleus quantum mechanically on the same level as the electrons. We investigate two intramolecular proton transfer reactions in organic molecules at temperatures down to 50 K to evaluate the performance of NEO-GRT by comparison to transition state theory and ring-polymer instanton theory. The KIEs computed with NEO-GRT agree with those calculated using ring-polymer instanton theory for the full-dimensional molecular systems at the same level of electronic structure theory. This agreement indicates that NEO-GRT captures the deep hydrogen tunneling effects, in contrast to transition state theory, which neglects such effects. Given its relatively low computational cost, NEO-GRT is a promising approach for predicting H/D KIEs in large organic and organometallic systems.

Hydrogen↗
NASA NTRS1985

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide - A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO2 similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO2 + O isotopic exchange, and a secondary NoMaD fractionation (delta O-17 = 0.97 + or - 0.09 delta O-18, with the O2 depleted in O-17 and O-18). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.

Heidenreich, J. E., III↗
DOE OSTI2025

Impact of the isotope effect on divertor detachment and pedestal structure in DIII-D

Dedicated H-mode hydrogen experiments have been conducted at DIII-D and are compared to similar deuterium plasmas under a range of divertor conditions, revealing significant effects of the isotope mass on divertor and pedestal conditions. H-mode confinement is found to be systematically lower in hydrogen and experiences a worse degradation with increased fueling. This coincides with a higher ne,sep in hydrogen for similar fueling rates. When ne,ped is matched in hydrogen and deuterium as are the ne and Te pedestal structures, the target conditions deviate strongly from each other. An analysis of two major factors in the pedestal structure, pedestal stability and neutral fueling, shows they are not sufficient to explain either the pedestal differences between isotopes or the hydrogen pedestal structure respectively. An analysis of hydrogen and deuterium density ramps demonstrates a 20% higher ion current and a 30% higher upstream density at detachment onset in hydrogen. The characteristics of target heat flux and divertor radiation are shown to change significantly with the isotope mass in each divertor operational regime. The results shown here indicate divertor conditions trend with ion mass in a manner beneficial for divertor performance in future devices.

Mattes, Ray [Univ. of Tennessee, Knoxville, TN (Un↗
DOE OSTI2023

Ten-Fold Solvent Kinetic Isotope Effect for the Nonradiative Relaxation of the Aqueous Ferrate(VI) Ion

Hypervalent iron intermediates have been invoked in the catalytic cycles of many metalloproteins, and thus, it is crucial to understand how the coupling between such species and their environment can impact their chemical and physical properties in such contexts. In this work, we take advantage of the solvent kinetic isotope effect (SKIE) to gain insight into the nonradiative deactivation of electronic excited states of the aqueous ferrate-(VI) ion. Here we observe an exceptionally large SKIE of 9.7 for the nanosecond-scale relaxation of the lowest energy triplet ligand field state to the ground state. Proton inventory studies demonstrate that a single solvent O-H bond is coupled to the ion during deactivation, likely due to the sparse vibrational structure of ferrate-(VI). Such a mechanism is consistent with that reported for the deactivation of f-f excited states of aqueous trivalent lanthanides, which exhibit comparably large SKIE values. This phenomenon is ascribed entirely to dissipation of energy into a higher overtone of a solvent acceptor mode, as any impact on the apparent relaxation rate due to a change in solvent viscosity is negligible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Isotope effects in dynamics of water isotopologues induced by core ionization at an x-ray free-electron laser

Dynamical response of water exposed to x-rays is of utmost importance in a wealth of science areas. We exposed isolated water isotopologues to short x-ray pulses from a free-electron laser and detected momenta of all produced ions in coincidence. By combining experimental results and theoretical modeling, we identify significant structural dynamics with characteristic isotope effects in H 2 O 2+ , D 2 O 2+ , and HDO 2+ , such as asymmetric bond elongation and bond-angle opening, leading to two-body or three-body fragmentation on a timescale of a few femtoseconds. A method to disentangle the sequences of events taking place upon the consecutive absorption of two x-ray photons is described. The obtained deep look into structural properties and dynamics of dissociating water isotopologues provides essential insights into the underlying mechanisms.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Use of the Magnetic Isotope Effect for Silicon Isotopomer Chemical Separation

The goal of the Phase I work was to develop a novel approach to silicon isotope separation that will use the difference in chemical reactivity of the three naturally-occurring silicon isotopes. The 'magnetic isotope effect' (MIE) will be employed to differentially react 29Si from 28Si and 30Si. The difference in reactivity to either directly deplete 29Si to the required sub-ppm levels or deplete 29Si sufficiently to allow final purification with distillation or centrifugation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Isotope effect in formaldehyde steam reforming on Pt/m-ZrO 2 : Insight into chemical promotion by alkalis

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO 2 . In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO 2 and H 2 . Alkali-doping of 2 wt% Pt/m-ZrO 2 increases catalyst basicity, which weakens the formate C-H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate nu(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H-to D-labeled formalde-hyde in TP-reaction/MS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Global Gyrokinetic Simulations of Isotope Effects under Ambipolar Electric Fields and Advances Toward Whole-Volume Modeling

We review global gyrokinetic simulation studies on plasma transport in the Large Helical Device using XGC-S. XGC-S is an extended version of X-point Gyrokinetic Code for stellarators and has been progressively verified throughout the code development process. Verification tests of neoclassical transport successfully demonstrate the generation of an ambipolar electric field due to ripple-trapped particles. We perform quasi-linear analyses of the ion temperature gradient mode under the influence of the ambipolar electric field. The results reveal that the ambipolar electric field and the heavy hydrogen component in mixed isotope plasmas can lead to the favorable isotope effect observed in recent deuterium experiments. We also present recent efforts in code development toward whole-volume simulations, including the helical divertor region. A mesh generation scheme based on field-line tracing and the construction of curved surfaces perpendicular to the magnetic field would be promising for global field calculations in the whole-volume simulations.

Basic Plasma Phenomena and Gas Discharges↗
NASA NTRS1989

The C-13/C-12 kinetic isotope effect for soil oxidation of methane at ambient atmospheric concentrations

During a survey of the Alaskan North Slope to estimate the isotopic composition and fluxes of methane (CH4) from the tundra, two sites were encountered that showed net methane consumption within flux chambers. Methane concentrations decreased from ambient (1.78 ppmv) by up to 50 percent, and the delta C-13 increased by up to 10 percent in the two chamber deployments showing CH4 consumption. CH4 consumption rates were measured to be 1.2 and 0.6 mg CH4/sq m per day; the corresponding carbon kinetic isotope effects (k13/k12) were 0.974 and 0.984, respectively.

King, Stagg L.↗
DOE OSTI2025

Kinetic Isotope Effect in the Radical Step-Growth Termination of On-Surface Synthesized Graphene Nanoribbons

Bottom-up on-surface synthesis has emerged as a versatile tool to access and finely tune the electronic structure of nanographenes. The controlled generation of reactive intermediates catalyzed and stabilized by a supporting substrate has enabled the design, assembly, and characterization of a wide range of exotic tailor-made quantum materials. Even under these tightly controlled conditions, the growth of extended structures remains limited by termination processes and undesired side reactions. Here, we identify an H atom transfer as one principal contributor to the radical step growth termination that limits the on-surface growth of N = 7 armchair graphene nanoribbons (7-AGNRs) on Au(111) surfaces. Analysis of 7-AGNR lengths grown from protiated and deuterated molecular precursors reveals a primary kinetic isotope effect of KIE ∼ 1.4. First-principles density functional theory calculations suggest that a concerted H atom transfer mechanism that involves the breaking of a C–H/D bond in the transition state is associated with radical chain termination.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

On the origin of the DIII-D L-H power threshold isotope effect

Abstract The increased low to high confinement mode (L to H-mode) power threshold P L H in DIII-D low collisionality hydrogen plasmas (compared to deuterium) is shown to result from lower impurity (carbon) content, consistent with reduced (mass-dependent) physical and chemical sputtering of graphite. Trapped gyro-Landau fluid (TGLF) quasilinear calculations and local non-linear gyrokinetic CGYRO simulations confirm stabilization of ion temperature gradient (ITG) driven turbulence by increased carbon ion dilution as the most important isotope effect. In the plasma edge, electron non-adiabaticity is also predicted to contribute to the isotope dependence of thermal transport and P L H , however its effect is subdominant compared to changes from impurity isotopic behavior. This L-H power threshold reduction with increasing carbon content at low collisionality is in stark contrast to high collisionality results, where additional impurity content appears to increase the power necessary for H-mode access.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1977

Inverse isotope effect and the x dependence of the superconducting transition temperature in PdHx and PdDx

First-principles electron-band-structure calculations and measured phonon properties are employed in a calculation of the concentration dependence of the superconducting transition temperatures for PdHx and PdDx, including the inverse isotope effect. Excellent agreement with the experimental results is obtained. Our model also gives a qualitative understanding of the enhanced transition temperatures in the palladium-noble-metal hydrides.

Klein, B. M.↗
NASA NTRS1989

Isotope effects in dense solid hydrogen - Phase transition in deuterium at 190 + or - 20 GPa

Raman measurements of solid normal deuterium compressed in a diamond-anvil cell indicate that the material undergoes a structural phase transformation at 190 + or - 20 GPa and 77 K. Spectroscopically, the transition appears analogous to that observed in hydrogen at 145 + or - 5 GPa. The large isotope effect on the transition pressure suggests there is a significant vibrational contribution to the relative stability of the solid phases of hydrogen at very high densities.

Hemley, R. J.↗
DOE OSTI2024

Position-specific kinetic isotope effects for nitrous oxide: a new expansion of the Rayleigh model

Nitrous oxide (N 2 O) is a potent greenhouse gas and the most significant anthropogenic ozone-depleting substance currently being emitted. A major source of anthropogenic N 2 O emissions is the microbial conversion of fixed nitrogen species from fertilizers in agricultural soils. Thus, understanding the enzymatic mechanisms by which microbes produce N 2 O has environmental significance. Measurement of the 15 N/ 14 N isotope ratios of N 2 O produced by purified enzymes or axenic microbial cultures is a promising technique for studying N 2 O biosynthesis. Typically, N 2 O-producing enzymes combine nitrogen atoms from two identical substrate molecules (NO or NH 2 OH). Position-specific isotope analysis of the central (N α ) and outer (N β ) nitrogen atoms in N 2 O enables the determination of the individual kinetic isotope effects (KIEs) for N α and N β , providing mechanistic insight into the incorporation of each nitrogen atom. Previously, position-specific KIEs (and fractionation factors) were quantified using the Rayleigh distillation equation, i.e., via linear regression of δ 15 N α or δ 15 N β against [–f In f / (1 – f)], where f is the fraction of substrate remaining in a closed system. This approach, however, is inaccurate for N α and N β because it does not account for fractionation at N α affecting the isotopic composition of substrate available for incorporation into the β position (and vice versa). Therefore, we developed a new expansion of the Rayleigh model that includes specific terms for fractionation at the individual N 2 O nitrogen atoms. By applying this Expanded Rayleigh model to a variety of simulated N 2 O synthesis reactions with different combinations of normal, inverse, and/or no KIEs at N α and N β , we demonstrate that our new model is both accurate and robust. We also applied this new model to two previously published datasets describing N 2 O production from NH 2 OH oxidation in a methanotroph culture (Methylosinus trichosporium) and N 2 O production from NO by a purified Histoplasma capsulatum (fungal) P450 NOR, demonstrating that the Expanded Rayleigh model is a useful tool in calculating position-specific fractionation for N 2 O synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗