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All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

The Age of Lunar South Circumpolar Craters Haworth, Shoemaker, Faustini, and Shackleton: Implications for Regional Geology, Surface Processes, and Volatile Sequestration

The interiors of the lunar south circumpolar craters Haworth, Shoemaker, Faustini, and Shackleton contain permanently shadowed regions (PSRs) and have been interpreted to contain sequestered volatiles including water ice. Altimetry data from the Lunar Orbiter Laser Altimeter (LOLA) onboard the Lunar Reconnaissance Orbiter provide a new means of examining the permanently shadowed interiors of these craters in unprecedented detail. In this study, we used extremely high-resolution gridded LOLA data of Haworth, Shoemaker, Faustini, and Shackleton to determine the size-frequency distributions and the spatial density of craters superposing their rims, inner slopes, and floors. Based on their population of superposed D greater than or equal to 2 km craters, Haworth, Shoemaker, and Faustini have pre-Nectarian formation ages. Shackleton is interpreted as having a Late Imbrian age on the basis of craters with diameter D greater than or equal to 0.5 km superposed on its rim. The local density of craters with sub-km diameters across our study area is strongly dependent on slope; because of its steep interior slopes, the lifetime of craters on the interior of Shackleton is limited. The slope-dependence of the small crater population implies that the population in this size range is controlled primarily by the rate at which craters are destroyed. This is consistent with the hypothesis that crater removal and resurfacing is a result of slopedependent processes such as diffusive mass wasting and seismic shaking, linked to micrometeorite and meteorite bombardment. Epithermal neutron flux data and UV albedo data show that these circumpolar PSRs, particularly Shoemaker, may have approximately 1-2% water ice by mass in their highly porous surface regolith, and that Shoemaker may have approximately 5% or more water ice by mass in the near subsurface. The ancient formation ages of Shoemaker, Faustini and Haworth, and the Late Imbrian (approximately 3.5 Ga) crater retention ages of their floors suggests that any water ice that might have been deposited in their permanently shadowed areas was insufficient to modify the superposed crater population since that time.

Circumpolar↗
DOE OSTI2022

Effect of Composition and Local Environment on CO 2 Adsorption on Nickel and Magnesium Oxide Solid Solutions

CO 2 adsorption energies on the (100) surfaces of a nickel oxide doped with Mg, magnesium oxide doped with Ni, and their 50:50 solid solution were calculated using density functional theory. The composition and atomic arrangement of the adsorption site was varied to understand how the local environment affects CO 2 adsorption and the basicity of the surfaces at the atomic level. The dispersive and electronic contributions to the adsorption energies were quantified, and the results indicate that the variation of the adsorption energy with adsorption site configuration and metal composition is dominated by electronic interactions. Interestingly, for magnesium oxide doped with nickel, a single substitution can create stronger CO 2 binding sites, which implies stronger basic sites, even though nickel oxide is less basic than magnesium oxide. The effect of double substitution at the binding site can be reasonably approximated by summing the effects of single substitutions. Furthermore, this work provides guidance for the preparation of metal oxides with tailored Lewis basicity.

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

A charged particle transport approximation for thick and thin plasmas

In this work, we will construct a simple method to be utilized in the interpretation of the properties of a thin plasma from a study of the transport of charged particles through it. We do so by first demonstrating how charged particle fluxes encode local plasma information in their spectra for sufficiently thick plasmas and then propose how to extend that analysis to the thin plasma limit where the extensive geometry cannot be neglected through arguments from scale separation. We provide a numerical treatment of the transport problem and demonstrate that it is in good agreement with the approximation we present. Finally, we utilize both the numerical solution and our novel approximation to study the impact of the extensive scale of the plasma on the yield and flux normalized high-energy neutron spectra resulting from the upscattering of charged fuel ions. Using this analysis, we show that (after controlling for fusion yield) for the same uniform densities and temperatures, larger plasmas have higher magnitude but softer reaction-in-flight (RIF) neutron spectra relative to smaller plasmas. This is because larger plasmas retain more knocked-on suprathermal ions within their bulk and can downscatter them to lower average energies, while smaller plasmas allow a larger fraction of high energy particles to “range out” of the system prior to substantial downscattering or inducing an RIF reaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1999

A New Probe of the Molecular Gas Content in Galaxies: Application to M101

Recent studies of nearby spiral galaxies suggest that photodissoiation regions (PDRS) are capable of producing much of the observed HI in galaxy disks. In that case, measurements of the observed HI column density and the far-ultraviolet (FUV) photon flux responsible for the photodissociation process provide a new probe of the volume density of the local underlying molecular hydrogen. We develop the method and apply it to the giant Scd spiral M101. The HI column density and amount of FUV emission have been measured for a sample of 35 candidate PDRs located throughout the disk of M101 using the Very Large Array and the Ultraviolet Imaging Telescope. We find that, after correction for the known gradient of metallicity in the Interstellar Medium (ISM) of M101 and for the extinction of the ultraviolet emission, molecular gas with a narrow range of density from 30-1000/ cubic cm is found near star-forming regions at all radii in the disk of M101 out to a distance of 12 seconds approximately equals 26 kpc, close to the photometric limit of R(sub 25) approximately equals 13.5 seconds. In this picture, the ISM is virtually all molecular in the inner parts of M101. The strong decrease of the HI column density in the inner disk of the galaxy at R(sub G) < 10 kpc is a consequence of a strong increase in the dust-to-gas ratio there, resulting in an increase of the H(sub 2) formation rate on grains and a corresponding disappearance of hydrogen in its atomic form.

Smith, Denise A.↗
NASA NTRS2019

Photoionization Calculations of the Radiation Force Due To Spectral Lines in AGNs

One of the main mechanisms that could drive mass outflows in active galactic nuclei (AGNs) is radiation pressure due to spectral lines. Although straightforward to understand, the actual magnitude of the radiation force is challenging to compute because the force depends on the physical conditions in the gas, as well as the strength, spectral energy distribution (SED), and geometry of the radiation field. We present results from our photoionization and radiation transfer calculations of the force multiplier, M(ξ, t), using the same radiation field to compute the gas photoionization and thermal balance. We assume low gas density (n = 104 per cu.cm) and column density (N ≤ 1017 per sq.cm), a Boltzmann distribution for the level populations, and the Sobolev approximation. Here, we describe results for two SEDs corresponding to an unobscured and obscured AGN in NGC 5548. Our main results are the following: (1) although M(ξ, t) starts to decrease with ξ for ξ gsim 1 as shown by others, this decrease in our calculations is relatively gradual and could be nonmonotonic as M(ξ, t) can increase by a factor of a few for ξ ≈ 10–1000; (2) at these same ξ for which the multiplier is higher than in previous calculations, the gas is thermally unstable by the isobaric criterion; (3) non-local thermodynamic equilibrium effects reduce M(t, ξ) by over two orders of magnitude for ξ gsim 100. The dynamical consequence of result (1) is that line driving can be important for ξ as high as 1000 when the LTE approximation holds, while result (2) provides a natural cloud formation mechanism that may account for the existence of narrow line regions. Result (3) suggests that line driving may not be important for ξ gsim 100 in tenuous plasma.

Dannen, Randall C.↗
DOE OSTI2020

Mott localization in the van der Waals crystal CrI 3 : A GGA+DMFT study

Using the generalized gradient approximation plus dynamical mean-field theory (GGA+DMFT) we confirm the importance of multi-orbital dynamical correlations in determining the paramagnetic insulating state of CrI 3 . Furthermore, while the ferromagnetic phase reveals weak electronic correlation effects due to strong spin-orbital polarization, the Mott insulating state of paramagnetic CrI 3 crystal is shown to be driven by the interplay between orbital-dependent one-electron lineshape and multi-orbital electronic interactions. To probe the paramagnetic Mott insulating state we performed x-ray absorption spectroscopy (XAS) measurements for the two structural phases of CrI 3 . Our study is relevant to understanding the orbital-selective electronic structure reconstruction of Mott insulators and should be applicable to other van der Waals bonded materials from bulk to the ultrathin limit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Density functional theory of water with the machine-learned DM21 functional

The delicate interplay between functional-driven and density-driven errors in density functional theory (DFT) has hindered traditional density functional approximations (DFAs) from providing an accurate description of water for over 30 years. Recently, the deep-learned DeepMind 21 (DM21) functional has been shown to overcome the limitations of traditional DFAs as it is free of delocalization error. To determine if DM21 can enable a molecular-level description of the physical properties of aqueous systems within Kohn–Sham DFT, we assess the accuracy of the DM21 functional for neutral, protonated, and deprotonated water clusters. Furthermore, we find that the ability of DM21 to accurately predict the energetics of aqueous clusters varies significantly with cluster size. Additionally, we introduce the many-body MB-DM21 potential derived from DM21 data within the many-body expansion of the energy and use it in simulations of liquid water as a function of temperature at ambient pressure. We find that size-dependent functional-driven errors identified in the analysis of the energetics of small clusters calculated with the DM21 functional result in the MB-DM21 potential systematically overestimating the hydrogen-bond strength and, consequently, predicting a more ice-like local structure of water at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1978

An iterative procedure for obtaining maximum-likelihood estimates of the parameters for a mixture of normal distributions

This paper addresses the problem of obtaining numerically maximum-likelihood estimates of the parameters for a mixture of normal distributions. In recent literature, a certain successive-approximations procedure, based on the likelihood equations, was shown empirically to be effective in numerically approximating such maximum-likelihood estimates; however, the reliability of this procedure was not established theoretically. Here, we introduce a general iterative procedure, of the generalized steepest-ascent (deflected-gradient) type, which is just the procedure known in the literature when the step-size is taken to be 1. We show that, with probability 1 as the sample size grows large, this procedure converges locally to the strongly consistent maximum-likelihood estimate whenever the step-size lies between 0 and 2. We also show that the step-size which yields optimal local convergence rates for large samples is determined in a sense by the 'separation' of the component normal densities and is bounded below by a number between 1 and 2.

Peters, B. C., Jr.↗
NASA NTRS1992

A three-dimensional hydrodynamic treatment of the hot dark matter cosmological scenario

The study computes the evolution of the hot dark matter (HDM) model containing both baryonic matter and dark matter for a post recombination Friedmann-Robertson-Walker universe. A locally valid Newtonian approximation is used to model a representative piece of the universe with size much less than the horizon. For the HDM model with the present chosen normalization, the hard X-ray (1-10 keV) radiation intensity is less than that in the observations (Wu et al., 1991) by a factor of 30. In agreement with other work, it is found that baryonic matter is slightly antibiased over dark matter on the cell scale, 0.5/h Mpc = 667 kpc. The HDM model with the present chosen parameters does not overproduce X-ray-luminous clusters, and there is a negative evolution in the late epochs in the sense that the number density of X-ray clusters was higher at 0.5 redshift than at 0 redshift at the brightest end.

Cen, Renyue↗
NASA NTRS1994

The heliospheric plasma sheet

High-resolution magnetic field and plasma data gathered by ISEE 3/ICE during several sector boundary crossings are used to investigate the narrow heliospheric current sheet (approximately equal 3 x 10 (exp 3) km to 10 (exp 4) km thick), together with the heliospheric plasma sheet in which it is embedded. The heliospheric plasma sheet region is identified by a significantly enhanced plasma beta caused by density enhancements and diminished magnetic field strength and is about 20 to 30 times the thickness of the current sheet. The thickness of the heliospheric plasma sheet is found to increase exponentially with its average proton density. The heliospheric current sheet is often displaced to one edge or the other of the heliospheric plasma sheet. Further, the point of maximum plasma beta in the plasma sheet, where the magnetic field strength is at a broad local minimum, is not colocated with the heliospheric current sheet. Within the plasma sheet, changes in the magnetic pressure are balanced by corresponding changes in the plasma thermal pressure as expected for a convected solar wind feature. In addition, observations show small pressure differences between the regions upstream and downstream of the plasma sheet, which are interpreted as causing the plasma sheet to move across the spacecraft.

Winterhalter, D.↗
NASA NTRS1993

Electron distributions in the inner Jovian magnetosphere: Voyager 1 observations

Using several improvements in the analysis of the observations of the Low Energy Charged Particle (LECP) experiment on Voyager 1, electron phase space densities in the inner Jovian magnetosphere (5 - 10 R(sub J) were first calculated at constant first and second invariants (represented by mu and K, respectively), based on the LECP measurements. The calculated electron phase space density profiles show that in the inner Jovian magnetosphere there exist evident time and longitude variations, energetic electron injections, and present radial transport and distributed losses. To study the radial and pitch angle diffusions of Jovian electrons, we have calculated the phase space densities in the K-L space. It is found that the electron population in the inner Jovian magnetosphere seems to consist of two components: electrons radially diffusing from a main external source and electrons generated from local sources. The radially diffusing electrons have a relatively time stationary and isotropic distribution, while the locally created electrons mainly concentrate around the equatorial plane and have relatively lower energies, in comparison with the inward diffusing electrons. Consequently, the sources of precipitation losses to the ionosphere must be primarily electrons transported from outer sources, and the major precipitations occur in the inner magnetosphere (L less than 7.5 R(sub J). In the inner Jovian magnetosphere (L = 5 to approximately 10 R(sub J)) it is estimated that for electrons with magnetic moment mu = 300 MeV/G, the diffusion coefficient D is roughly 10(exp -8) to approximately 10(exp -6) R(exp 2)(sub J)/s, and the lifetime against the diffusion losses is of the order of 10(exp 4) to approximately 10(exp 6) s.

Ye, G.↗
NASA NTRS2006

Shuttle Damage/Repair from the Perspective of Hypersonic Boundary Layer Transition - Experimental Results

An overview is provided of the experimental wind tunnel program conducted at the NASA Langley Research Center Aerothermodynamics Laboratory in support of an agency-wide effort to prepare the Shuttle Orbiter for Return-to-Flight. The effect of an isolated protuberance and an isolated rectangular cavity on hypersonic boundary layer transition onset on the windward surface of the Shuttle Orbiter has been experimentally characterized. These experimental studies were initiated to provide a protuberance and cavity effects database for developing hypersonic transition criteria to support on-orbit disposition of thermal protection system damage or repair. In addition, a synergistic experimental investigation was undertaken to assess the impact of an isolated mass-flow entrainment source (simulating pyrolysis/outgassing from a proposed tile repair material) on boundary layer transition. A brief review of the relevant literature regarding hypersonic boundary layer transition induced from cavities and localized mass addition from ablation is presented. Boundary layer transition results were obtained using 0.0075-scale Orbiter models with simulated tile damage (rectangular cavities) of varying length, width, and depth and simulated tile damage or repair (protuberances) of varying height. Cavity and mass addition effects were assessed at a fixed location (x/L = 0.3) along the model centerline in a region of near zero pressure gradient. Cavity length-to-depth ratio was systematically varied from 2.5 to 17.7 and length-to-width ratio of 1 to 8.5. Cavity depth-to-local boundary layer thickness ranged from 0.5 to 4.8. Protuberances were located at several sites along the centerline and port/starboard attachment lines along the chine and wing leading edge. Protuberance height-to-boundary layer thickness was varied from approximately 0.2 to 1.1. Global heat transfer images and heating distributions of the Orbiter windward surface using phosphor thermography were used to infer the state of the boundary layer (laminar, transitional, or turbulent). Test parametrics include angles-of-attack of 30 deg and 40 deg, sideslip angle of 0 deg, freestream Reynolds numbers from 0.02x106 to 7.3x106 per foot, edge-to-wall temperature ratio from 0.4 to 0.8, and normal shock density ratios of approximately 5.3, 6.0, and 12 in Mach 6 air, Mach 10 air, and Mach 6 CF4, respectively. Testing to simulate the effects of ablation from a proposed tile repair concept indicated that transition was not a concern. The experimental protuberance and cavity databases highlighted in this report were used to formulate boundary layer transition correlations that were an integral part of an analytical process to disposition observed Orbiter TPS damage during STS- 114.

Horvath, Thomas J.↗
DOE OSTI2023

Semiclassical theory and the Koopman-van Hove equation *

Abstract The phase space Koopman-van Hove (KvH) equation can be derived from the asymptotic semiclassical analysis of partial differential equations. Semiclassical theory yields the Hamilton–Jacobi equation for the complex phase factor and the transport equation for the amplitude. These two equations can be combined to form a nonlinear semiclassical version of the KvH equation in configuration space. There is a natural injection of configuration space solutions into phase space and a natural projection of phase space solutions onto configuration space. Hence, every solution of the configuration space KvH equation satisfies both the semiclassical phase space KvH equation and the Hamilton–Jacobi constraint. For configuration space solutions, this constraint resolves the paradox that there are two different conserved densities in phase space. For integrable systems, the KvH spectrum is the Cartesian product of a classical and a semiclassical spectrum. If the classical spectrum is eliminated, then, with the correct choice of Jeffreys–Wentzel–Kramers–Brillouin (JWKB) matching conditions, the semiclassical spectrum satisfies the Einstein–Brillouin–Keller quantization conditions which include the correction due to the Maslov index. However, semiclassical analysis uses different choices for boundary conditions, continuity requirements, and the domain of definition. For example, use of the complex JWKB method allows for the treatment of tunneling through the complexification of phase space. Finally, although KvH wavefunctions include the possibility of interference effects, interference is not observable when all observables are approximated as local operators on phase space. Observing interference effects requires consideration of nonlocal operations, e.g. through higher orders in the asymptotic theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1995

Focusing of nonducted whistlers by the equatorial anomaly

Impulsive ELF/VLF electric field bursts observed by the vector electric field instrument (VEFI) on the Dynamics Explorer 2 (DE 2) satellite on almost every crossing of the geomagnetic equator in the evening hours are interpreted as originating in lightning discharges. These signals that peak in intensity near the magnetic equator are observed within 5-20 deg latitude of the geomagnetic equator at altitudes of 300-500 km with amplitudes of the order of approximately mV/m in the 512- or 1024-Hz frequency band of the VEFI instrument. Whistler-mode ELF/VLF wave propagation through a horizontally stratified ionosphere predicts strong attenuation of subionospheric signals reaching the equator at low altitudes. However, ray tracing analysis shows that the presence of the equatorial density anomaly, commonly observed in the upper ionosphere during evening hours, leads to the focusing of the wave energy from lightning near the geomagnetic equator at low altitudes, thus accounting for all observed aspects of the phenomenon. The observations presented here indicate that during certain hours in the evening, almost all the energy input from lightning discharges entering the ionosphere at less than 30 deg latitude remains confined to a small region (in altitude and latitude) near the geomagnetic equator. The net wideband electric field, extrapolated from the observed electric field values in the 512- to 1024-Hz band, can be approximately 10 mV/m or higher. These strong electric fields generated in the ionosphere by lightning at local evening times may be important for the equatorial electrodynamics of the ionosphere.

Sonwalkar, Vikas S.↗
NASA NTRS1995

Modeling and numerical simulation of microwave pulse propagation in air breakdown environment

It is shown that ionization occurs wherever the field intensity of the pulse exceeds the local breakdown threshold field of the background air. The produced plasma then attenuates the pulse and gives rise to a tail erosion phenomenon that plays the primary role in limiting the energy transfer of the pulse from source to destination. A theoretical model describing the propagation of an intense microwave pulse in an air breakdown environment is developed that includes the possible focusing effect introduced by either using phase array antennas or the other arrangements. The self-consistent description of the propagation process is provided by a set of two modal equations. These include a continuity equation (Poynting's equation) for the energy density of the pulse and a rate equation of the electron density. A forward wave approximation is used to simplify Poynting's equation, and a semiempirical formula is used for the ionization frequency, nu(sub i). This frequency provides the coupling between the two modal equations, and is used to express the electron rate equation explicitly. In terms of the relevant parameters of the atmosphere, these two equations are normalized for numerical analysis of pulse propagation in the atmosphere. The dependencies of the propagation characteristics of the pulse on intensity, frequency, width, and shape of the pulse are determined. The numerical simulations lead to a useful empirical relation p(exp 3)w = alpha = constant, where p and w are the incident power and width of the pulse and alpha depends on the percentage of pulse energy transferred from the source point to a destined position. The density distribution of the pulse's self-generated plasma is also evaluated. The results also show that for ionization caused by a single unfocused microwave pulse transmitted upwards from the ground, the maximum electron density produced at, for example, 50 km altitude is limited by the tail erosion effect to below 10(exp 6) cm(exp -3). Repetitive pulse and focused beam approaches are also examined. Both approaches can increase the maximum electron density by no more than an order of magnitude. A scheme using two obliquely propagating pulses intersecting at the destined height, e.g. 50 km, is considered. It is shown that the electron density generated at the lowest intersecting position can easily reach a value of 6.6 x 10(exp 8) cm(exp -3), which is considered to be high enough for artificial ionospheric mirror (AIM) application.

Kim, J.↗
NASA NTRS2019

Meteoroids at the Moon: Orbital Properties, Surface Vaporization, and Impact Ejecta Production

We use a dynamical model to characterize the monthly and yearly variations of the lunar meteoroid environment for meteoroids originating from short and long‐period comets and the main‐belt asteroids. Our results show that if we assume the meteoroid mass flux of 43.3 tons per day at Earth, inferred from previous works, the mass flux of meteoroids impacting the Moon is 30 times smaller, approximately 1.4 tons per day, and shows variations of the order of 10% over a year. The mass flux difference is due to the combined effect of the smaller cross‐section of the Moon (factor of 13.46) and Earth's larger gravitational focusing (factor of 2–2.5). The lunar surface is vaporized by these impactors at an average impact vaporization flux of 11.6 × 10−16 g·cm−2·s−1, providing a significant source for the rarefied lunar exosphere. Our model predicts acceptable vaporization rates and reproduces the local time dependence of observations of the dust ejecta cloud, measured by the Lunar Dust Experiment on board NASA's Lunar Atmosphere and Dust Environment (LADEE) satellite. However, the predicted density of the lunar ejecta cloud is four orders of magnitude larger than reported values by LADEE. This discrepancy might be attributed to a much lower yield from meteoroid impacts on fluffy lunar regolith and/or a lower detection efficiency of the LADEE dust detector. We suggest an upper limit of 30 cm per million years for the soil gardening rate from small meteoroids.

Petr Pokorny↗
DOE OSTI2023

Investigation of local distortion effects on X-ray absorption of ferroelectric perovskites from first principles simulations

Understanding the role of ferroelectric polarization in modulating the electronic and structural properties of crystals is critical for advancing these materials for overcoming various technological and scientific challenges. However, due to difficulties in performing experimental methods with the required resolution, or in interpreting the results of methods therein, the nanoscale morphology and response of these surfaces to external electric fields has not been properly elaborated. Here, in this work, we investigate the effect of ferroelectric polarization and local distortions in a BaTiO 3 perovskite, using two widely used computational approaches which treat the many-body nature of X-ray excitations using different philosophies, namely the many-body, delta-self-consistent-field determinant (mb-ΔSCF) and the Bethe–Salpeter equation (BSE) approaches. We show that in agreement with our experiments, both approaches consistently predict higher excitations of the main peak in the O–K edge for the surface with upward polarization. However, the mb-ΔSCF approach mostly fails to capture the L 2,3 separations at the Ti–L edge, due to the absence of spin–orbit coupling in Kohn–Sham density functional theory (KS-DFT) at the generalized gradient approximation level. On the other hand, and most promising, we show that application of the GW/BSE approach successfully reproduces the experimental XAS, both the relative peak intensities as well as the L 2,3 separations at the Ti–L edges upon ferroelectric switching. Thus simulated XAS is shown to be a powerful method for capturing the nanoscale structure of complex materials, and we underscore the need for many-body perturbation approaches, with explicit consideration of core-hole and multiplet effects, for capturing the essential physics in these systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Libration of hydroxyl groups in layered aluminum (oxy)hydroxides and other material analogs: insights from inelastic neutron scattering and theory

We analyzed the hydroxyl librational signatures of five structurally related aluminum (oxy)hydroxides, using inelastic neutron scattering (INS) and plane-wave lattice dynamics simulations. A clear trend across these aluminum-containing phases illustrates the relationship between hydrogen bonding, local atomic structure, and the spectral location and profile of the librational bands. The INS spectra have been compared to previous optical spectroscopy and computational studies, highlighting the complementary nature of the INS technique. Taking into account other structurally or chemically related material analogs, we have identified a correlation between a blueshift (to higher energy) of the upper librational band edge and the geometry of the hydrogen bond interactions, mirroring (with opposite correlation) the well-known redshift in the intramolecular O–H stretching energy with increasing hydrogen bond strength. For hydroxyl groups that do not participate in hydrogen bonding effectively, the bending librations occur at lower energies and hybridize with metal–oxygen lattice modes. Standard density functional theory approximations, including dispersion corrections, struggle to correctly predict vibrational frequencies of motions dominated by H but perform well for metal–oxygen modes, allowing us to make detailed mode assignments in several cases, including a demonstration of how layer-to-layer disorder in boehmite hydrogen bond orientations is reflected in the sharp but minor low energy peaks (at ∼70–80 meV) of the INS spectrum.

Wang, Hsiu-Wen [Oak Ridge National Laboratory (ORN↗