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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A drift kinetic model for the expander region of a magnetic mirror

Here, we present a drift kinetic model for the free expansion of a thermal plasma out of a magnetic nozzle. This problem relates to plasma space propulsion systems, natural environments such as the solar wind, and end losses from the expander region of mirror magnetically confined fusion concepts such as the gas dynamic trap. The model incorporates trapped and passing orbit types encountered in the mirror expander geometry and maps to an upstream thermal distribution. This boundary condition and quasineutrality require the generation of an ambipolar potential drop of ~5T e /e, forming a thermal barrier for the electrons. The model for the electron and ion velocity distributions and fluid moments is confirmed with data from a fully kinetic simulation. Finally, the model is extended to account for a population of fast sloshing ions arising from neutral beam heating within a magnetic mirror, again resulting in good agreement with a corresponding kinetic simulation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Protein folding from heterogeneous unfolded state revealed by time-resolved X-ray solution scattering

One of the most challenging tasks in biological science is to understand how a protein folds. In theoretical studies, the hypothesis adopting a funnel-like free-energy landscape has been recognized as a prominent scheme for explaining protein folding in views of both internal energy and conformational heterogeneity of a protein. Despite numerous experimental efforts, however, comprehensively studying protein folding with respect to its global conformational changes in conjunction with the heterogeneity has been elusive. Here we investigate the redox-coupled folding dynamics of equine heart cytochrome c (cyt-c) induced by external electron injection by using time-resolved X-ray solution scattering. A systematic kinetic analysis unveils a kinetic model for its folding with a stretched exponential behavior during the transition toward the folded state. With the aid of the ensemble optimization method combined with molecular dynamics simulations, we found that during the folding the heterogeneously populated ensemble of the unfolded state is converted to a narrowly populated ensemble of folded conformations. These observations obtained from the kinetic and the structural analyses of X-ray scattering data reveal that the folding dynamics of cyt-c accompanies many parallel pathways associated with the heterogeneously populated ensemble of unfolded conformations, resulting in the stretched exponential kinetics at room temperature. This finding provides direct evidence with a view to microscopic protein conformations that the cyt-c folding initiates from a highly heterogeneous unfolded state, passes through still diverse intermediate structures, and reaches structural homogeneity by arriving at the folded state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A novel path to runaway electron mitigation via deuterium injection and current-driven MHD instability

Relativistic electron (RE) beams at high current density (low safety factor, qa) yet very low free-electron density accessed with D2 secondary injection in the DIII-D and JET tokamak are found to exhibit large-scale MHD instabilities that benignly terminate the RE beam. In JET, this technique has enabled termination of MA-level RE currents without measurable first-wall heating. This scenario thus offers an unexpected alternate pathway to achieve RE mitigation without collisional dissipation. Benign termination is explained by two synergistic effects. First, during the MHD-driven RE loss events both experiment and MHD orbit-loss modeling supports a significant increase in the wetted area of the RE loss. Second, as previously identified at JET and DIII-D, the fast kink loss timescale precludes RE beam regeneration and the resulting dangerous conversion of magnetic to RE kinetic energy. During the termination, the RE kinetic energy is lost to the wall, but the current fully transfers to the cold bulk thus enabling benign Ohmic dissipation of the magnetic energy on longer timescales via a conventional current quench. Hydrogenic (D2) secondary injection is found to be the only injected species that enables access to the benign termination. D2 injection: 1) facilitates access to low qa in existing devices (via reduced collisionality & resistivity), 2) minimizes the RE avalanche by ‘purging’ the high-Z atoms from the RE beam, 3) drives recombination of the background plasma, reducing the density and Alfven time, thus accelerating the MHD growth. Furthermore, this phenomenon is found to be accessible when crossing the low qa stability boundary with rising current, falling toroidal field, or contracting minor radius - the latter being the expected scenario for vertically unstable RE beams in ITER. While unexpected, this path scales favorably to fusion-grade tokamaks and offers a novel RE mitigation scenario in principle accessible with the day-one disruption mitigation system (DMS) of ITER.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Applicability of semiclassical theories in the strong-field plasma regime

For many purposes, classical plasma dynamics models can work surprisingly well, even for strong electromagnetic fields, approaching the Schwinger critical fields, and high frequencies, approaching the Compton frequency. However, the applicability of classical models tends to depend rather sensitively on the details of the problem. In the present paper, we study the specific case of plasma oscillations to draw a line between the classical and quantum relativistic regimes. Here, due to the field geometry of study, mechanisms like radiation reaction and Breit-Wheeler pair production, which tend to be important for electromagnetic fields, are rather effectively suppressed. Moreover, we find that the polarization current due to the electron spin is generally negligible for frequencies below the Compton frequency, compared with the free current, whose magnitude is well-approximated by the classical Vlasov theory. However, we show that pair creation due to the Schwinger mechanism can sometimes be important for surprisingly modest field strengths, of the order of 10% of the critical field or even smaller. A rough guideline for when the classical Vlasov theory can be applied is given.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

BioXTAS RAW 2 : new developments for a free open-source program for small-angle scattering data reduction and analysis

BioXTAS RAW is a free open-source program for reduction, analysis and modelling of biological small-angle scattering data. Here, the new developments in RAW version 2 are described. These include improved data reduction using pyFAI ; updated automated Guinier fitting and D max finding algorithms; automated series ( e.g. size-exclusion chromatography coupled small-angle X-ray scattering or SEC-SAXS) buffer- and sample-region finding algorithms; linear and integral baseline correction for series; deconvolution of series data using regularized alternating least squares ( REGALS ); creation of electron-density reconstructions using electron density via solution scattering ( DENSS ); a comparison window showing residuals, ratios and statistical comparisons between profiles; and generation of PDF reports with summary plots and tables for all analysis. Furthermore, there is now a RAW API, which can be used without the graphical user interface (GUI), providing full access to all of the functionality found in the GUI. In addition to these new capabilities, RAW has undergone significant technical updates, such as adding Python 3 compatibility, and has entirely new documentation available both online and in the program.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Magnon heat transport in a two-dimensional Mott insulator

Whether or not anomalies in the thermal conductivity in insulating cuprates can be attributed to antiferromagnetic order and magnons in a 2D Mott insulator remains an intriguing open question. To shed light on this issue, we investigate the thermal conductivity $\kappa$ and its relationship with the specific heat $c_v$ in the half-filled 2D single-band Hubbard model, using the numerically exact determinant quantum Monte Carlo algorithm and maximum entropy analytic continuation. At low temperatures where the charge degrees of freedom are gapped-out and $c_v$ exhibits a clear magnon peak, we observe that thermal conductivity $\kappa$ also tends to form a peak at similar temperatures. Reducing temperature further produces a sharp upturn in $\kappa$, associated with an increasing mean-free path. Here we identify this as the high-temperature side of the anomalous peak in insulating cuprates, where the mean-free path eventually is cut-off by other scattering effects, including phonons, disorder, and physical size. Different scattering effects in our model are identified and analyzed in the thermal diffusivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Observations on Microbunching of Electrons in Laser-Driven Plasma Accelerators and Free-Electron Lasers

The periodic longitudinal density modulation of relativistic electrons at the resonant wavelength (microbunching) is a fundamental aspect of free-electron lasers (FELs). In one case, microbunching fractions reached 20% at saturation of a self-amplified spontaneous emission (SASE) FEL resulting in gains of 1 million at 530 nm. In that experiment the $\textit{z}$-dependent gain of coherent optical transition radiation (COTR) was also measured. In laser-driven plasma accelerators (LPAs), microbunching at visible wavelengths has also been recently reported as evidenced by significant COTR enhancements measured in near-field and far-field images on a single shot for the first time. An analytical model for COTR interferometry (COTRI) addresses both cases. The broadband microbunching observed in the LPA case could act as a seed for a SASE FEL experiment with tunability in principle over the visible regime.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Controls on Soil Organic Matter Degradation and Subsequent Greenhouse Gas Emissions Across a Permafrost Thaw Gradient in Northern Sweden

Warming-induced permafrost thaw could enhance microbial decomposition of previously stored soil organic matter (SOM) to carbon dioxide (CO 2 ) and methane (CH 4 ), one of the most significant potential feedbacks from terrestrial ecosystems to the atmosphere in a changing climate. The environmental parameters regulating microbe-organic matter interactions and greenhouse gas (GHG) emissions in northern permafrost peatlands are however still largely unknown. The objective of this work is to understand controls on SOM degradation and its impact on porewater GHG concentrations across the Stordalen Mire, a thawing peat plateau in Northern Sweden. Here, we applied high-resolution mass spectrometry to characterize SOM molecular composition in peat soil samples from the active layers of a Sphagnum-dominated bog and rich fen sites in the Mire. Microbe-organic matter interactions and porewater GHG concentrations across the thaw gradient were controlled by aboveground vegetation and soil pH. An increasingly high abundance of reduced organic compounds experiencing greater humification rates due to enhanced microbial activity were observed with increasing thaw, in parallel with higher CH 4 and CO 2 porewater concentrations. Bog SOM however contained more Sphagnum-derived phenolics, simple carbohydrates, and organic- acids. The low degradation of bog SOM by microbial communities, the enhanced SOM transformation by potentially abiotic mechanisms, and the accumulation of simple carbohydrates in the bog sites could be attributed in part to the low pH conditions of the system associated with Sphagnum mosses. We show that Gibbs free energy of C half reactions based on C oxidation state for OM can be used as a quantifiable measure for OM decomposability and quality to enhance current biogeochemical models to predict C decomposition rates. We found a direct association between OM chemical diversity and δ 13 C-CH 4 in peat porewater; where higher substrate diversity was positively correlated with enriched δ 13 C-CH 4 in fen sites. Oxidized sulfur-containing compounds, produced by Sphagnum, were further hypothesized to control GHG emissions by acting as electron acceptors for a sulfate-reducing electron transport chain, inhibiting methanogenesis in peat bogs. These results suggest that warming-induced permafrost thaw might increase organic matter lability, in subset of sites that become wetlands, and shift biogeochemical processes toward faster decomposition with an increasing proportion of carbon released as CH 4 .

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Size- and Temperature-Dependent Suppression of Phonon Thermal Conductivity in Carbon Nanotube Thermoelectric Films

Heat transport in nanoscale carbon materials such as carbon nanotubes and graphene is normally dominated by phonons. Here, measurements of in-plane thermal conductivity, electrical conductivity, and thermopower are presented from 77–350 K on two films with thickness <100 nm formed from semiconducting single-walled carbon nanotubes. These measurements are made with silicon–nitride membrane thermal isolation platforms. The two films, formed from disordered networks of tubes with differing tube and bundle size, have very different thermal conductivity. One film matches a simple model of heat conduction assuming constant phonon velocity and mean free path, and 3D Debye heat capacity with a Debye temperature of 770 K. The second film shows a more complicated temperature dependence, with a dramatic drop in a relatively narrow window near 200 K where phonon contributions to thermal conductivity essentially vanish. This causes a corresponding large increase in thermoelectric figure-of-merit at the same temperature. A better understanding of this behavior can allow significant improvement in thermoelectric efficiency of these low-cost earth-abundant, organic electronic materials. Finally, heat and charge conductivity near room temperature is also presented as a function of doping, which provides further information on the interaction of dopant molecules and phonon transport in disordered nanotube films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Origin of the background absorption in carbon nanotubes: Phonon-assisted excitonic continuum

Excitonic effects in 1D semiconductors can be qualitatively different from those in higher dimensions. In particular, the Sommerfeld factor, the ratio of the above-band-edge excitonic continuum absorption to free electron-hole pair generation, has been shown to be less than 1 (suppressed) in 1D systems while it is larger than 1 (enhanced) in 2D and 3D systems. Strong continuum suppression indeed exists in semiconducting single-wall carbon nanotubes, a prototypical 1D semiconductor. However, absorption spectra for carbon nanotubes are typically fit with a combination of Lorentzians and a polynomial background baseline with little physical meaning. We performed absorption measurements in aligned single-chirality (6,5) carbon nanotube films. The obtained spectra were fit with our theoretical model obtained by solving the Boltzmann scattering equation involving fifty-nine different types of transitions among three different types of quasiparticles. Specifically, we took into account microscopic interactions between photons, phonons, and excitons, including their dispersions, which unambiguously demonstrated that the background absorption is due to phonon-assisted transitions from the semiconductor vacuum to finite-momentum continuum states of excitons. The excellent agreement we obtained between experiment and theory suggests that our numerical technique can be seamlessly extended to compute strongly out-of-equilibrium many-body dynamics and time-resolved spectra in low-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermodynamics and kinetics of solution combustion synthesis: Ni(NO 3 ) 2 + fuels systems

Solution combustion synthesis (SCS) utilizes exothermic self-propagating reactions to prepare nanoscale materials that can be used widely in energy, electronics, and biomedical technologies and other applications. SCS is a specific variety of a more general combustion synthesis (CS) method. Investigations of the thermodynamics, kinetics, and the mechanisms of SCS reactions, are not as well studied as the other CS processes. This work reports on a systematic study of the thermodynamics and kinetics of SCS reactions involving Ni(NO 3 ) 2 , an oxidizer, and either glycine (C 2 H 5 NO 2 ) or hexamethylenetetramine (HMT, C 6 H 12 N 4 ) as fuels. A thermodynamic modeling approach, based on the Gibbs free energy minimization principle, is applied to the simultaneous calculations of the adiabatic temperatures and compositions of the equilibrium products. Our calculations reveal the influence of fuel-to-oxidizer ratio, amount of water, and the oxygen in air on the combustion temperature under adiabatic conditions and the composition of the resulting products. We have, in turn, measured the combustion temperature and phase composition of products and compared them with the calculations. Variations of drying times for the solutions yield precursor gels with varying water contents. This approach enables the manipulation of combustion parameters and confirms the use of calculated activation energies for reactions using the Merzhanov-Khaikin method. Here, the results show that SCS reactions in fuel-lean solutions producing NiO have higher activation energy in contrast to reactions with fuel-rich solutions that form Ni. Reduction of activation energies due to the increase in the fuel-to-oxidizer ratio could be related to the observed change of the rate-limiting stages of the endothermic decomposition of the individual reactants to the exothermic decomposition of coordinate compounds formed between the reactants.

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

Quantitative relationships between film morphology, charge carrier dynamics, and photovoltaic performance in bulk-heterojunction binary vs. ternary acceptor blends

Addressing pertinent and perplexing questions regarding why nonfullerene acceptors (NFAs) promote higher power conversion efficiencies (PCEs) than traditional fullerenes and how photoactive bulk heterojunction (BHJ) film morphology, charge photogeneration, and recombination dynamics dictate solar cell performance have stimulated many studies of polymer solar cells (PSCs), yet quantitative relationships remain limited. Better understanding in these areas offers the potential to advance materials design and device engineering, afford higher PCEs, and ultimate commercialization. Here we probe quantitative relationships between BHJ film morphology, charge carrier dynamics, and photovoltaic performance in model binary and ternary blend systems having a wide bandgap donor polymer, a fullerene, and a promising NFA. We show that optimal PC 71 BM incorporation in a PBDB-TF:ITIC-Th binary system matrix retains the original π-face-on orientation, ITIC-Th crystallinity and BHJ film crystallite dimensions, and reduces film upper surface ITIC-Th segregation. Such morphology changes together simultaneously increase hole (μ h ) and electron (μ e ) mobilities, facilitate light-activated ITIC-Th to PC 71 BM domain electron delocalization, reduce free charge carrier (FC) bimolecular recombination (BR) within PBDB-TF:ITIC-Th mixed regions, and increase FC extraction pathways viaPBDB-TF:PC 71 BM pairs. The interplay of these effects yields significantly enhanced inverted cell short-circuit current density (J SC ), fill factor (FF), and PCE. Unexpectedly, we also find that excessive PC 71 BM in the PBDB-TF:ITIC-Th binary system alters the PBDB-TF orientation to π-edge-on, increases large scale PC 71 BM-rich aggregations and BHJ upper surface PC 71 BM composition. Further, these morphology changes increase parasitic decay processes such as intersystem crossing from photoexcited PC 71 BM, compromising the J SC , FF, and PCE metrics. ITIC-Th X-ray diffraction reveals a unique sidechain-dominated molecular network with previously unknown sidechain-end group stacking, rationalizing the STEM and GIWAXS results, photophysics, and the high μ e . DFT computation reveals charge transfer networks within ITIC-Th crystallites, supporting excited-state electron delocalization from ITIC-Th to PC 71 BM. This structure–property understanding leads to a newly reported NFA blend with PCE near 17%.

14 SOLAR ENERGY↗
DOE OSTI2022

TIA: A forward model and analyzer for Talbot interferometry experiments of dense plasmas

Interferometry is one of the most sensitive and successful diagnostic methods for plasmas. However, owing to the design of most common interferometric systems, the wavelengths of operation and, therefore, the range of densities and temperatures that can be probed are severely limited. Talbot–Lau interferometry offers the possibility of extending interferometry measurements to x-ray wavelengths by means of the Talbot effect. While there have been several proof-of-concept experiments showing the efficacy of this method, it is only recently that experiments to probe High Energy Density (HED) plasmas using Talbot–Lau interferometry are starting to take place. To improve these experimental designs, we present here the Talbot-Interferometry Analyzer (TIA) tool, a forward model for generating and postprocessing synthetic x-ray interferometry images from a Talbot–Lau interferometer. Although TIA can work with any two-dimensional hydrodynamic code to study plasma conditions as close to reality as possible, this software has been designed to work by default with output files from the hydrodynamic code FLASH, making the tool user-friendly and accessible to the general plasma physics community. Here, the model has been built into a standalone app, which can be installed by anyone with access to the MATLAB runtime installer and is available upon request to the authors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Broad Distribution of Local Polar States Generates Large Electrothermal Properties in Pb-Free Relaxor Ferroelectrics

Electrothermal energy conversion provides attractive solutions for global energy management, such as energy harvesting from waste heat using pyroelectric energy conversion (PEC) and efficient cooling of portable electronics or data servers using the electrocaloric effect. Relaxor ferroelectrics are attractive for electrothermal energy conversion because of their large pyroelectric coefficients over a wide temperature range. Although Pb-based relaxors are well-known, toxicity concerns have mandated the intense search for Pb-free alternatives. Here, we engineered (Ba,Ca)TiO 3 -based relaxors based on a multisite doping strategy, which show promising electrothermal performance, viz. a maximum PEC efficiency of 14% and electrocaloric refrigeration capacity of 115 J/kg. Using local-scale structural analysis, we provide an atomistic model for large electrothermal properties in the newly designed Pb-free ferroelectrics, whereby a temperature-independent continuous distribution of cation displacement directions creates easy pathways for microscopic polarization reorientation. This research provides key structural insight for future atomic-scale engineering of environmentally sustainable ferroelectrics in energy applications.

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

Large-volume CdZnTe bar detectors characterized by laser-induced transient currents

In this work, we studied the free-carrier transport properties and space-charge formation/polarization in a CdZnTe bar-shaped radiation detector using the Laser-Induced Transient Current technique. We found out that a steady-state space charge ranging from 8 x 10 8 to 2.1 x 10 9 cm -3 is formed throughout the detector at about 0.5 s following biasing. The measured current waveforms were modeled by Monte Carlo simulations after taking into account the electric and weighting fields inside the detector and shielding box. Modeling of the unpolarized waveforms revealed an exceptionally high electron mobility-lifetime product μ e τ e ≥0.095cm 2 V -1 . The observed formation of positive space charge in the biased detector and linear scaling of the current waveform shapes on applied bias revealed that the detector polarization is attributed to carrier injection at the anode. In conclusion, measurements in pulsed and DC bias in modified electrode geometry proved the surface-charge formation.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

A future of inertial confinement fusion without laser-plasma instabilities

From the beginning of inertial confinement fusion (ICF) research, laser-plasma instabilities excited by narrowband lasers have limited the hydrodynamic design space of all laser-based approaches to inertial fusion energy (IFE). With advances in broadband laser technologies, the next generation of ICF drivers will likely have large bandwidth that is engineered to mitigate laser-plasma instabilities, thereby expanding the hydrodynamic design space to include both robust high yields (>200−MJ) with large-energy laser systems (>4 MJ) and high gains (>10) with moderate-energy laser facilities (<2 MJ). State-of-the-art simulations indicate that laser bandwidths of a few percent are required to mitigate instabilities for IFE-relevant conditions. To test these models and demonstrate that high-bandwidth lasers mitigate laser-plasma instabilities, the Fourth-generation Laser for Ultrabroadband eXperiments will be used with the OMEGA Laser System. The goal is to provide the community with the confidence to invest in a multiple-beam high-bandwidth laser facility that will demonstrate the necessary ablation pressures for robust direct-drive ignition without detrimental levels of hot electrons that degrade the implosion performance. It is important to recognize that the highest performing ICF implosions will likely never be completely LPI free because of the significant advantages to maximizing the laser intensity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

BuildingSync® v.2.7.0 (released 9.11.2025) [SWR-18-28]

BuildingSync® is a building data exchange schema to better enable integration between software tools and building data workflows. The schema's original use case was focused on commercial building energy audits; however, several additional use cases have been realized including building energy modeling and more high-level generic building data exchange. Version 2.7.0 adds new elements for file attachment feature and FederalBuilding, and generalizes usage of Optional Elements (e.g. EquipmentCondition, EquipmentID) to all assets/systems. BuildingSync helps streamline the data exchange process, improving the value of the data, minimizing duplication of effort for subsequent building data collection efforts (including audits), and facilitating the achievement of greater energy efficiency. This in done in part by standardizing on (a) reporting audits in an electronic format, (b) tracking proposed, implemented, and discarded energy conservation measures, and (c) storing building characteristics (at multiple levels) for audits, benchmarking, and building energy analysis. BuildingSync has several documents and tools available to help users understand how to best leverage BuildingSync. The list below are only a subset of the resources available. If new resources are discovered, then feel free to create a new pull request with the additions. Generic BuildingSync information is available on the DOE website and the project website. BuildingSync Examples - These examples are kept up to date and show a wide range of implementations. Any new update to BuildingSync is required to pass validation on these example files. BuildingSync Use Case Validator allows for users to determine if their instance complies with a specific use case for BuildingSync by checking if the required elements are implemented in an uploaded instance. An API is also provided for automated integration into other tools. Also, the website contains an easy way to view the entirety of the schema and how elements relate to the Building Exchange Data Exchange Specification. The Validator is open sourced here Use Case TestSuite provides a Python package for easier generation of BuildingSync use cases. BuildingSync use cases depend on the generation of schematron documents, which is time-consuming and difficult to implement well. The TestSuite allows users to define a use case using a more palatable CSV template, which it then turns into a Schematron document. The source code is available here. BuildingSync to OpenStudio/EnergyPlus. The translator is open sourced here. This project will translate a Level 1 (and partial Level 2) ASHRAE Energy Audit to a fully defined OpenStudio and EnergyPlus model. This project is in early Beta testing and any feedback is welcome!

Long, Nicholas [National Renewable Energy Lab. (NR↗
DOE OSTI2022

Hydrated Anions: From Clusters to Bulk Solution with Quasi-Chemical Theory

The interactions of hydrated ions with molecular and macromolecular solution and interface partners are strong on a chemical energy scale. Here we recount the foremost ab initio theory for the evaluation of the hydration free energies of ions, namely, quasi-chemical theory (QCT). We focus on anions, particularly halides but also the hydroxide anion, because they have been outstanding challenges for all theories. For example, this work supports understanding the high selectivity for F – over Cl – in fluoride-selective ion channels despite the identical charge and the size similarity of these ions. QCT is built by the identification of inner-shell clusters, separate treatment of those clusters, and then the integration of those results into the broader-scale solution environment. Recent work has focused on a close comparison with mass-spectrometric measurements of ion-hydration equilibria. We delineate how ab initio molecular dynamics (AIMD) calculations on ion-hydration clusters, elementary statistical thermodynamics, and electronic structure calculations on cluster structures sampled from the AIMD calculations obtain just the free energies extracted from the cluster experiments. That theory–experiment comparison has not been attempted before the work discussed here, but the agreement is excellent with moderate computational effort. This agreement reinforces both theory and experiment and provides a numerically accurate inner-shell contribution to QCT. The inner-shell complexes involving heavier halides display strikingly asymmetric hydration clusters. Asymmetric hydration structures can be problematic for the evaluation of the QCT outer-shell contribution with the polarizable continuum model (PCM). Nevertheless, QCT provides a favorable setting for the exploitation of PCM when the inner-shell material shields the ion from the outer solution environment. For the more asymmetrically hydrated, and thus less effectively shielded, heavier halide ions clustered with waters, the PCM is less satisfactory. We therefore investigate an inverse procedure in which the inner-shell structures are sampled from readily available AIMD calculations on the bulk solutions. This inverse procedure is a remarkable improvement; our final results are in close agreement with a standard tabulation of hydration free energies, and the final composite results are independent of the coordination number on the chemical energy scale of relevance, as they should be. Finally, a comparison of anion hydration structure in clusters and bulk solutions from AIMD simulations emphasize some differences: the asymmetries of bulk solution inner-shell structures are moderated compared with clusters but are still present, and inner hydration shells fill to slightly higher average coordination numbers in bulk solution than in clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗