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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

The NASA/AFRL Meter Class Autonomous Telescope

For the past decade, the NASA Orbital Debris Program Office (ODPO) has relied on using various ground-based telescopes in Chile to acquire statistical survey data as well as photometric and spectroscopic data of orbital debris in geosynchronous Earth orbit (GEO). The statistical survey data have been used to supply the Orbital Debris Engineering Model (ORDEM) v.3.0 with debris detections in GEO to better model the environment at altitudes where radar detections are limited. The data produced for the statistical survey ranged from 30 to 40 nights per year, which only accounted for ~10% of the possible observing time. Data collection was restricted by ODPO resources and weather conditions. In order to improve the statistical sampling in GEO, as well as observe and sample other orbits, NASA's ODPO with support from the Air Force Research Laboratory (AFRL), has constructed a new observatory dedicated to orbital debris - the Meter Class Autonomous Telescope (MCAT) on Ascension Island. This location provides MCAT with the unique ability to access targets orbiting at an altitude of less than 1,000 km and low inclinations (< 20 deg). This orbital regime currently has little to no coverage by the U.S. Space Surveillance Network. Unlike previous ODPO optical assets, the ability to operate autonomously will allow rapid response observations of break-up events, an observing mode that was only available via radar tasking prior to MCAT's deployment. The primary goal of MCAT is to statistically characterize GEO via daily tasking files uploaded from ODPO. These tasking files define which operating mode to follow, providing the field center, rates, and/or targets to observe over the entire observing period. The system is also capable of tracking fast-moving targets in low Earth orbit (LEO), middle Earth orbit (MEO), as well as highly eccentric orbits like geostationary transfer orbits. On 25 August 2015, MCAT successfully acquired scientific first light, imaging the Bug Nebula and tracked objects in LEO, MEO, and GEO. NASA is working towards characterizing the system and thoroughly testing the integrated hardware and software control to achieve fully autonomous operations by late 2016. This paper will review the history and current status of the MCAT project, the details of the telescope system, and its five currently manifested operating modes.

Cowardin, H.↗
DOE OSTI2022

On the Statistics of Elsasser Increments in Solar Wind and Magnetohydrodynamic Turbulence

In this Letter we investigate the dependency with scale of the empirical probability distribution functions (PDF) of Elsasser increments using large sets of WIND data (collected between 1995 and 2017) near 1 au. The empirical PDF are compared to the ones obtained from high-resolution numerical simulations of steadily driven, homogeneous reduced MHD turbulence on a 2048 3 rectangular mesh. A large statistical sample of Alfvénic increments is obtained by using conditional analysis based on the solar wind average properties. The PDF tails obtained from observations and numerical simulations are found to have exponential behavior in the inertial range, with an exponential decrement that satisfies power laws of the form α l ∝ l –μ , where l is the scale size, with μ between 0.17 and 0.25 for observations and 0.43 for simulations. PDF tails were extrapolated assuming their exponential behavior extends to arbitrarily large increments in order to determine structure function scaling laws at very high orders. Our results point to potentially universal scaling laws governing the PDF of Elsasser increments and to an alternative approach to investigate high-order statistics in solar wind observations.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1993

X-ray emission from a complete sample of Abell clusters of galaxies

The Rosat all sky survey is used to investigate the X-ray properties of a sample of Abell clusters with measured redshifts and accurate positions. The sample comprises the 145 clusters within a 561 square degree region at high galactic latitude. The mean redshift is 0.17. The sample mean exposure time is higher than average and its mean galactic column density is very low. These together produce a flux limit of about 4.2 x 10(exp -13) erg/sq cm/s in the 0.5 to 2.5 keV energy band. By analyzing the excess of positive fluctuations of the X-ray flux at the cluster positions, compared with the fluctuations of randomly drawn background fields, it is possible to extend these results below the nominal flux limit. It is found that 80 of richness R equal to or greater than 0 and 86 of R equal to or greater than 1 clusters are X-ray emitters with fluxes above 1.10 to the power of minus 13 erg/sq cm/s. Nearly 90 of the clusters meeting the requirements to be in Abell's statistical sample emit above the same level. It is concluded that almost all Abell clusters are real clusters and the Abell catalogue is not strongly contaminated by projection effects. The Kaplan-Meier product limit estimator is used to calculate the cumulative X-ray luminosity function. It is shown that the shape of the luminosity functions are similar for different richness classes, but the characteristic luminosities of richness 2 clusters are about twice of those of richness 1 clusters which are in turn about twice of those of richness zero clusters. This result is another manifestation of the luminosity richness relation for Abell cluster.

Briel, Ulrich G.↗
DOE OSTI2024

Statistical data analysis of x-ray spectroscopy data enabled by neural network accelerated Bayesian inference

Bayesian inference applied to x-ray spectroscopy data analysis enables uncertainty quantification necessary to rigorously test theoretical models. However, when comparing to data, detailed atomic physics and radiation transfer calculations of x-ray emission from non-uniform plasma conditions are typically too slow to be performed in line with statistical sampling methods, such as Markov Chain Monte Carlo sampling. Furthermore, differences in transition energies and x-ray opacities often make direct comparisons between simulated and measured spectra unreliable. Here, we present a spectral decomposition method that allows for corrections to line positions and bound–bound opacities to best fit experimental data, with the goal of providing quantitative feedback to improve the underlying theoretical models and guide future experiments. In this work, we use a neural network (NN) surrogate model to replace spectral calculations of isobaric hot-spots created in Kr-doped implosions at the National Ignition Facility. The NN was trained on calculations of x-ray spectra using an isobaric hot-spot model post-processed with Cretin, a multi-species atomic kinetics and radiation code. The speedup provided by the NN model to generate x-ray emission spectra enables statistical analysis of parameterized models with sufficient detail to accurately represent the physical system and extract the plasma parameters of interest.

47 OTHER INSTRUMENTATION↗
NASA NTRS1993

X-ray emission from a complete sample of Abell clusters of galaxies

The ROSAT All-Sky Survey (RASS) is used to investigate the X-ray properties of a complete sample of Abell clusters with measured redshifts and accurate positions. The sample comprises the 145 clusters within a 561 square degree region at high galactic latitude. The mean redshift is 0.17. This sample is especially well suited to be studied within the RASS since the mean exposure time is higher than average and the mean galactic column density is very low. These together produce a flux limit of about 4.2 x 10(exp -13) erg/sq cm/s in the 0.5 to 2.5 keV energy band. Sixty-six (46%) individual clusters are detected at a significance level higher than 99.7% of which 7 could be chance coincidences of background or foreground sources. At redshifts greater than 0.3 six clusters out of seven (86%) are detected at the same significance level. The detected objects show a clear X-ray luminosity -- galaxy count relation with a dispersion consistent with other external estimates of the error in the counts. By analyzing the excess of positive fluctuations of the X-ray flux at the cluster positions, compared with the fluctuations of randomly drawn background fields, it is possible to extend these results below the nominal flux limit. We find 80% of richness R greater than or = 0 and 86% of R greater than or = 1 clusters are X-ray emitters with fluxes above 1 x 10(exp -13) erg/sq cm/s. Nearly 90% of the clusters meeting the requirements to be in Abell's statistical sample emit above the same level. We therefore conclude that almost all Abell clusters are real clusters and the Abell catalog is not strongly contaminated by projection effects. We use the Kaplan-Meier product limit estimator to calculate the cumulative X-ray luminosity function. We show that the shape of the luminosity functions are similiar for different richness classes, but the characteristic luminosities of richness 2 clusters are about twice those of richness 1 clusters which are in turn about twice those of richness 0 clusters. This result is another manifestation of the luminosity -- richness elation for Abell clusters.

Briel, Ulrich G.↗
NASA NTRS2017

Refinement of Objective Motion Cueing Criteria Investigation Based on Three Flight Tasks

The objective of this paper is to refine objective motion cueing criteria for commercial transport simulators based on pilots' performance in three flying tasks. Actuator hardware and software algorithms determine motion cues. Today, during a simulator qualification, engineers objectively evaluate only the hardware. Pilot inspectors subjectively assess the overall motion cueing system (i.e., hardware plus software); however, it is acknowledged that pinpointing any deficiencies that might arise to either hardware or software is challenging. ICAO 9625 has an Objective Motion Cueing Test (OMCT), which is now a required test in the FAA's part 60 regulations for new devices, evaluating the software and hardware together; however, it lacks accompanying fidelity criteria. Hosman has documented OMCT results for a statistical sample of eight simulators which is useful, but having validated criteria would be an improvement. In a previous experiment, we developed initial objective motion cueing criteria that this paper is trying to refine. Sinacori suggested simple criteria which are in reasonable agreement with much of the literature. These criteria often necessitate motion displacements greater than most training simulators can provide. While some of the previous work has used transport aircraft in their studies, the majority used fighter aircraft or helicopters. Those that used transport aircraft considered degraded flight characteristics. As a result, earlier criteria lean more towards being sufficient, rather than necessary, criteria for typical transport aircraft training applications. Considering the prevalence of 60-inch, six-legged hexapod training simulators, a relevant question is "what are the necessary criteria that can be used with the ICAO 9625 diagnostic?" This study adds to the literature as follows. First, it examines well-behaved transport aircraft characteristics, but in three challenging tasks. The tasks are equivalent to the ones used in our previous experiment, allowing us to directly compare the results and add to the previous data. Second, it uses the Vertical Motion Simulator (VMS), the world's largest vertical displacement simulator. This allows inclusion of relatively large motion conditions, much larger than a typical training simulator can provide. Six new motion configurations were used that explore the motion responses between the initial objective motion cueing boundaries found in a previous experiment and what current hexapod simulators typically provide. Finally, a sufficiently large pilot pool added statistical reliability to the results.

motion simulation↗
DOE OSTI2017

The Statistics of Radio Astronomical Polarimetry: Disjoint, Superposed, and Composite Samples

A statistical framework is presented for the study of the orthogonally polarized modes of radio pulsar emission via the covariances between the Stokes parameters. To accommodate the typically heavy-tailed distributions of single-pulse radio flux density, the fourth-order joint cumulants of the electric field are used to describe the superposition of modes with arbitrary probability distributions. The framework is used to consider the distinction between superposed and disjoint modes, with particular attention to the effects of integration over finite samples. If the interval over which the polarization state is estimated is longer than the timescale for switching between two or more disjoint modes of emission, then the modes are unresolved by the instrument. The resulting composite sample mean exhibits properties that have been attributed to mode superposition, such as depolarization. Because the distinction between disjoint modes and a composite sample of unresolved disjoint modes depends on the temporal resolution of the observing instrumentation, the arguments in favor of superposed modes of pulsar emission are revisited, and observational evidence for disjoint modes is described. In principle, the four-dimensional covariance matrix that describes the distribution of sample mean Stokes parameters can be used to distinguish between disjoint modes, superposed modes, and a composite sample of unresolved disjoint modes. More comprehensive and conclusive interpretation of the covariance matrix requires more detailed consideration of various relevant phenomena, including temporally correlated subpulse modulation (e.g., jitter), statistical dependence between modes (e.g., covariant intensities and partial coherence), and multipath propagation effects (e.g., scintillation and scattering).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

A Workflow for Accelerating Multimodal Data Collection for Electrodeposited Films

Abstract Future machine learning strategies for materials process optimization will likely replace human capital-intensive artisan research with autonomous and/or accelerated approaches. Such automation enables accelerated multimodal characterization that simultaneously minimizes human errors, lowers costs, enhances statistical sampling, and allows scientists to allocate their time to critical thinking instead of repetitive manual tasks. Previous acceleration efforts to synthesize and evaluate materials have often employed elaborate robotic self-driving laboratories or used specialized strategies that are difficult to generalize. Herein we describe an implemented workflow for accelerating the multimodal characterization of a combinatorial set of 915 electroplated Ni and Ni–Fe thin films resulting in a data cube with over 160,000 individual data files. Our acceleration strategies do not require manufacturing-scale resources and are thus amenable to typical materials research facilities in academic, government, or commercial laboratories. The workflow demonstrated the acceleration of six characterization modalities: optical microscopy, laser profilometry, X-ray diffraction, X-ray fluorescence, nanoindentation, and tribological (friction and wear) testing, each with speedup factors ranging from 13–46x. In addition, automated data upload to a repository using FAIR data principles was accelerated by 64x.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Microstructure modeling of nuclear structural materials: Recent progress and future directions

Modeling and simulation of microstructures are essential to understand the complex responses and behaviors of nuclear materials in extreme environments. The needs to assess the extended life operation as well as the growing interest in accelerating nuclear materials development and qualification have stimulated the use of high-fidelity multiscale models aided by empirical and ab initio data. This paper reviews the role of various models across different length and time scales in investigating irradiation effects on microstructure evolution and degradation, in particular the embrittlement caused by radiation induced or enhanced formation of nanoscale chemical heterogeneities. The strength and limitations of these models, including classical rate theories, cluster dynamics, phase-field methods, and atomistic models informed by ab initio energies, are discussed with seminal examples. Challenges regarding the lack of thermo-kinetic data and theoretical treatments considering chemical complexities and magnetic excitations, as well as the stabilizing effect by excess point defects in nuclear structural materials are presented, along with potential solutions based on ab initio informed surrogate energy models and statistical sampling by Monte Carlo simulations. Further, the review then highlights the opportunities to leverage the advantages of different methods by establishing hybrid models by shared variables or coupled codes and applications. Finally, the review concludes with forward-looking remarks on how the use of physics-based models can aid the improvement of machine-learning models of property degradation and vice versa.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A numerical study of the meso-structure variability in the compaction process of prepreg platelet molded composites

Compaction deformations in a thermoplastic composite system molded from chopped prepreg platelets were analyzed to obtain statistical distributions of local distortions that define the final consolidated meso-structure. This study provides an insight into and allows quantification of the intrinsic geometric variability of the composite meso-structure that controls the variability of the effective composite mechanical properties. A two-phase viscoelastic finite element model was utilized to treat the behavior of molten prepreg platelets, which were assumed to be incompressible and inextensible in the fiber direction during processing. A two-step simulation procedure with discretely modeled platelets and platelet-to-platelet contacts is proposed. The analysis begins with a drop simulation of the uncontrolled material deposition followed by a 3D finite element analysis of the preform compaction and bulk material flow. The proposed model provides a method for generating a composite meso-structure ab initio starting from a statistical sampling of the initial conditions for platelet deposition. The predicted platelet thickness distribution, intra-platelet fiber waviness and out-of-plane platelet undulations were found to be in good agreement with experimental measurements. An estimate of the volume of resin pockets was inferred from the compaction simulation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Massively parallel Monte Carlo for many-particle simulations on GPUs

Current trends in parallel processors call for the design of efficient massively parallel algorithms for scientific computing. Parallel algorithms for Monte Carlo simulations of thermodynamic ensembles of particles have received little attention because of the inherent serial nature of the statistical sampling. In this paper, we present a massively parallel method that obeys detailed balance and implement it for a system of hard disks on the GPU. We reproduce results of serial high-precision Monte Carlo runs to verify the method. This is a good test case because the hard disk equation of state over the range where the liquid transforms into the solid is particularly sensitive to small deviations away from the balance conditions. On a Tesla K20, our GPU implementation executes over one billion trial moves per second, which is 148 times faster than on a single Intel Xeon E5540 CPU core, enables 27 times better performance per dollar, and cuts energy usage by a factor of 13. With this improved performance we are able to calculate the equation of state for systems of up to one million hard disks. These large system sizes are required in order to probe the nature of the melting transition, which has been debated for the last forty years. In this paper we present the details of our computational method, and discuss the thermodynamics of hard disks separately in a companion paper.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2013

Use of nanoindentation technique for a better understanding of the fracture toughness of Strombus gigas conch shell

In this work the nanochemical properties of the composite organomineral biomaterial constituting Strombus gigas conch shell are studied by means of dynamic mechanical analyses associated to nanoidentation technique. The measurements are performed on shell samples presenting different surface orientations relative to the growth axis of the conch shell. The influence of the organic component of the biomaterial on its nanomechanical properties is also investigated by studying fresh and dried S. gigas conch shells. Monocrystalline aragonite is used as a reference. For the understanding of nanochemical behaviour, special attention is paid to the pop in events observed on the load/displacement curves which results from nanofractures' initiation and propagation occuring during the load process. In order to better understand the mechanical properties systematic studies of the structure and morphology are performed using scanning electron microscopy, atomic force microscopy and X-ray diffractometry. The hardness and Young's modulus values measured on bio aragonite samples are close to those of the aragonite mineral standard. This surprising result shows that, H and E values are not related to the bio composition and lamellar structure of the bio aragonite. However, it was found that the organic layer and the micro architecture strongly influence the nanofracture initiation and propagation processes in the samples. Statistic study of the pop-in events can help to predict the macroscopic mechanical behaviour of the material. - Highlights: ► Nanomechanical properties of Strombus gigas conch shell ► Low influence of the crossed lamellar structure on H and E values at the nano scale ► Strong influence of the crossed lamellar on nanocracks initiation ► Correlation between mechanical behaviors at the macro and nano scales.

36 MATERIALS SCIENCE↗
DOE OSTI2014

First elevated-temperature performance testing of coated particle fuel compacts from the AGR-1 irradiation experiment

In the AGR-1 irradiation experiment, 72 coated-particle fuel compacts were taken to a peak burnup of 19.5% fissions per initial metal atom with no in-pile failures. This paper discusses the first post-irradiation test of these mixed uranium oxide/uranium carbide fuel compacts at elevated temperature to examine the fuel performance under a simulated depressurized conduction cooldown event. A compact was heated for 400 h at 1600 degrees C. Release of 85Kr was monitored throughout the furnace test as an indicator of coating failure, while other fission product releases from the compact were periodically measured by capturing them on exchangeable, water-cooled deposition cups. No coating failure was detected during the furnace test, and this result was verified by subsequent electrolytic deconsolidation and acid leaching of the compact, which showed that all SiC layers were still intact. However, the deposition cups recovered significant quantities of silver, europium, and strontium. Based on comparison of calculated compact inventories at the end of irradiation versus analysis of these fission products released to the deposition cups and furnace internals, the minimum estimated fractional losses from the compact during the furnace test were 1.9 x 10-2 for silver, 1.4 x 10-3 for europium, and 1.1 x 10-5 for strontium. Other post-irradiation examination of AGR-1 compacts indicates that similar fractions of europium and silver may have already been released by the intact coated particles during irradiation, and it is therefore likely that the detected fission products released from the compact in this 1600 degrees C furnace test were from residual fission products in the matrix. Gamma analysis of coated particles deconsolidated from the compact after the heating test revealed that silver content within each particle varied considerably; a result that is probably not related to the furnace test, because it has also been observed in other as-irradiated AGR-1 compacts. X-ray imaging of selected particles was performed to examine the internal microstructure. This examination revealed variable irradiation performance of the coating layers, but sufficient statistical sampling is not yet available to identify any possible correlation to variation in individual particle fission product retention.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

Empirically Optimized One-Electron Pseudopotential for the Hydrated Electron: A Proof-of-Concept Study

Mixed quantum-classical molecular dynamics simulations have been important tools for studying the hydrated electron. They generally use a one-electron pseudopotential to describe the interactions of an electron with the water molecules. Furthermore, this approximation shows both the strength and weakness of the approach. On the one hand, it enables extensive statistical sampling and large system sizes that are not possible with more accurate ab initio molecular dynamics methods. On the other hand, there has (justifiably) been much debate about the ability of pseudopotentials to accurately and quantitatively describe the hydrated electron properties. These pseudopotentials have largely been derived by fitting them to ab initio calculations of an electron interacting with a single water molecule. In this paper, we present a proof-of-concept demonstration of an alternative approach in which the pseudopotential parameters are determined by optimizing them to reproduce key experimental properties. Specifically, we develop a new pseudopotential, using the existing TBOpt model as a starting point, which correctly describes the hydrated electron vertical detachment energy and radius of gyration. In addition to these properties, this empirically optimized model displays a significantly modified solvation structure, which improves, for example, the prediction of the partial molar volume.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Advanced Potential Energy Surfaces for Molecular Simulation

Advanced potential energy surfaces are defined as theoretical models that explicitly include many-body effects that transcend the standard fixed-charge, pairwise-additive paradigm typically used in molecular simulation. However, several factors relating to their software implementation have precluded their widespread use in condensed-phase simulations: the computational cost of the theoretical models, a paucity of approximate models and algorithmic improvements that can ameliorate their cost, underdeveloped interfaces and limited dissemination in computational code bases that are widely used in the computational chemistry community, and software implementations that have not kept pace with modern high-performance computing (HPC) architectures, such as multicore CPUs and modern graphics processing units (GPUs). Here in this Feature Article we review recent progress made in these areas, including well-defined polarization approximations and new multipole electrostatic formulations, novel methods for solving the mutual polarization equations and increasing the MD time step, combining linear-scaling electronic structure methods with new QM/MM methods that account for mutual polarization between the two regions, and the greatly improved software deployment of these models and methods onto GPU and CPU hardware platforms. Finally, we have now approached an era where multipole-based polarizable force fields can be routinely used to obtain computational results comparable to state-of-the-art density functional theory while reaching sampling statistics that are acceptable when compared to that obtained from simpler fixed partial charge force fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Crystal Orientation and Defect Mapping in Electron-Beam-Sensitive Zeolites with Near-Axis Transmission Kikuchi Diffraction

Porous materials are vital in catalysis, energy conversion, and environmental remediation. Understanding structural heterogeneity in zeolites is key to linking synthesis, framework intergrowths, and catalytic performance, yet current methods for phase identification and spatial mapping lack sufficient resolution or throughput. We present a high-throughput approach using near-axis transmission Kikuchi diffraction in a scanning electron microscope, achieving high phase and spatial resolution for electron-beam-sensitive zeolites, including ZSM-5 and, for the first time, Zeolite A. Here, this method enables direct visualization of intergrowth features that critically affect catalytic and adsorption behavior, bridging the gap between ensemble-averaged X-ray diffraction and high-resolution but low-throughput transmission electron microscopy. Combining nanoscale mapping with statistical sampling is highly suited for machine-learning pipelines guiding new structure function understanding and could be extended to other beam-sensitive porous materials such as metal–organic or covalent–organic frameworks.

crystallography↗
DOE OSTI2021

Actinide Molten Salts: A Machine-Learning Potential Molecular Dynamics Study

We know that actinide molten salts represent a class of important materials in nuclear energy. Understanding them at a molecular level is critical to proper and optimal design of relevant technological applications. Yet, owing to the complexity of electronic structure due to the 5f orbitals, computational studies of heavy elements in condensed phases using ab initio potentials to study the structure and dynamics of these elements embedded in molten salts are difficult. This lack of efficient computational protocols makes it difficult to obtain information on properties that require extensive statistical sampling like transport. To tackle this problem, we adopted a machine-learning approach to study ThCl 4 -NaCl and UCl 3 -NaCl binary systems. The machine-learning potential, with the density functional theory accuracy, allows us to obtain long molecular dynamics trajectories (ns) for large systems (10 3 atoms) at a considerably low computing cost, thereby efficiently gaining information about their bonding structures, thermodynamics, and dynamics at a range of temperature. We observed a considerable change in the coordination environments of actinide elements and their characteristic coordination-sphere lifetime. Our study also suggests that actinides in molten salts may not follow well known entropy-scaling laws.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations

In this paper, we present a perspective on the computational determination of entropy and its effects and consequences on heterogeneous catalysis. Special attention is paid to the role of anharmonicity and the deviations from the standard harmonic oscillator approximations which can fail to provide a reliable assessment of entropy. To address these challenges, advanced methodologies are needed that can explicitly account for these thermodynamic drivers through the appropriate statistical sampling of reactive free energy surfaces. We discuss where anharmonicity should be expected, where it has been observed from a theoretical perspective, and the methods currently employed to address it. We concentrate on three types of systems where we have observed major, nonnegligible anharmonic effects: (1) supported nanoparticles, where the migration of metal atoms, complexes, and entire clusters exhibit anharmonic behavior in their dynamic motion; (2) porous solids where confinement effects distort potential energy surfaces and hinder molecular motions resulting in large entropic terms; and (3) solid/liquid interfaces, where interactions between solvent molecules and adsorbed species can result in large solvent organization free energy and unique reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗