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At least 1,423 records · Page 79

Green functions in stochastic field theory

Functional representations are reviewed for the generating function of Green functions of stochastic problems stated either with the use of the Fokker-Planck equation or the master equation. Both cases are treated in a unified manner based on the operator approach similar to quantum mechanics. Solution of a second-order stochastic differential equation in the framework of stochastic field theory is constructed. Ambiguities in the mathematical formulation of stochastic field theory are discussed. The Schwinger-Keldysh representation is constructed for the Green functions of the stochastic field theory which yields a functional-integral representation with local action but without the explicit functional Jacobi determinant or ghost fields.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

On-the-fly response function generation method for composite coarse mesh

The hybrid stochastic deterministic transport code COMET, based on the incident response expansion theory, is used to model reactor cores with high fidelity and formidable computational speed. COMET models a reactor core using a library of incident flux response expansion coefficients that are pre computed for all the unique lattice cells (e.g., fuel assemblies, reflector blocks, etc.) in the core. In order to further improve its computational efficiency in pre-calculating the response library a new response function generation method is developed to compute the response functions for the composite coarse meshes made of a smaller set of unique lattices on the fly within the COMET's deterministic transport core sweep. The efficiency is achieved by eliminating a number of unique lattices that can be made up from the reduced set of unique meshes on the fly. The numerical process consists of the following steps. First, the boundary condition on composite coarse mesh boundaries is projected onto the expansion basis to compute the incident flux moments on external surfaces of all the basic (reduced set of unique) coarse meshes. Secondly, the deterministic sweeping solver in COMET is used to converge on the outgoing/incoming flux expansion moments crossing interfaces between the basic coarse meshes. Thirdly, the response functions for the composite coarse meshes are constructed as a superposition on the fly. The new response function generation method was tested on 88 composite coarse meshes consisting of CANDU fuel bundles and moderator blocks. It was found that response functions generated by the new method agree very well with those generated by direct Monte Carlo calculations. The average and maximum relative differences in the surface-to-surface response coefficients computed by the two methods are 0.10% and 0.20%, respectively. Similarly, the average and maximum relative differences in the response fission densities are 0.13% and 0.43%, respectively. These discrepancies are within one standard deviation of the stochastic uncertainties. The new method is five times faster than the original direct Monte Carlo method. The size of the response function library for the new method is five times smaller than that for the original method, leading to significantly less requirement for the computer hard drive space and memory. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Cognition may link cortical IGFBP5 levels with motor function in older adults

Alzheimer’s disease and related disorders (ADRD) may manifest cognitive and non-cognitive phenotypes including motor impairment, suggesting a shared underlying biology. We tested the hypothesis that five cortical proteins identified from a gene network that drives AD and cognitive phenotypes are also related to motor function in the same individuals. We examined 1208 brains of older adults with motor and cognitive assessments prior to death. Cortical proteins were quantified with SRM proteomics and we collected indices of AD and other related pathologies. A higher level of IGFBP5 was associated with poorer motor function proximate to death but AK4, HSPB2, ITPK1 and PLXNB1 were unrelated to motor function. The association of IGFBP5 with motor function was unrelated to the presence of indices of brain pathologies. In contrast, the addition of a term for cognition attenuated the association of IGFBP5 with motor function by about 90% and they were no longer related. These data lend support for the idea that unidentified cortical proteins like IGFBP5, which may not manifest a known pathologic footprint, may contribute to motor and cognitive function in older adults.

59 BASIC BIOLOGICAL SCIENCES↗

Assessment of Methods to Consolidate Iodine-Loaded Silver-Functionalized Silica Aerogel

The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, Ag 0 -functionalized silica aerogels, shows great promise as a potential replacement for Ag-bearing mordenites because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag0-functionalized silica aerogels to a durable SiO 2 -based waste form makes this aerogel an attractive choice for sequestering radioiodine. This report provides a preliminary assessment of the methods that can be used to consolidate iodine-loaded Ag 0 -functionalized silica aerogels into a final waste form. In particular, it focuses on experimental investigation of densification of as prepared Ag 0 - functionalized silica aerogels powders, with or without organic moiety and with or without sintering additive (colloidal silica), with three commercially available techniques: 1) hot uniaxial pressing (HUP), 2) hot isostatic pressing (HIP), and 3) spark plasma sintering (SPS). The densified products were evaluated with helium gas pycnometer for apparent density, with the Archimedes method for apparent density and open porosity, and with high-resolution scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification and distribution of individual elements. The preliminary investigation of HUP, HIP, and SPS showed that these sintering methods can effectively consolidate powders of Ag 0 -functionalized silica aerogel into products of near-theoretical density. Also, removal of organic moiety and adding 5.6 mass% of colloidal silica to Ag0-functionalized silica aerogel powders before processing provided denser products. Furthermore, the ram travel data for SPS indicated that rapid consolidation of powders can be performed at temperatures below 950°C.

Ag-Functionalized Silica Aerogel↗

Experimental Evaluation of PV Inverter Anti-Islanding with Grid Support Functions in Multi-Inverter Island Scenarios

As PV and other DER systems are connected to the grid at increased penetration levels, island detection may become more challenging for two reasons: 1.) In islands containing many DERs, active inverter-based anti-islanding methods may have more difficulty detecting islands because each individual inverter's efforts to detect the island may be interfered with by the other inverters in the island. 2.) The increasing numbers of DERs are leading to new requirements that DERs ride through grid disturbances and even actively try to regulate grid voltage and frequency back towards nominal operating conditions. These new grid support requirements may directly or indirectly interfere with anti-islanding controls. This report describes a series of tests designed to examine the impacts of both grid support functions and multi-inverter islands on anti-islanding effectiveness. Crucially, the multi-inverter anti-islanding tests described in this report examine scenarios with multiple inverters connected to multiple different points on the grid. While this so-called 'solar subdivision' scenario has been examined to some extent through simulation, this is the first known work to test it using hardware inverters. This was accomplished through the use of power hardware-in-the-loop (PHIL) simulation, which allows the hardware inverters to be connected to a real-time transient simulation of an electric power system that can be easily reconfigured to test various distribution circuit scenarios. The anti-islanding test design was a modified version of the unintentional islanding test in IEEE Standard 1547.1, which creates a balanced, resonant island with the intent of creating a highly challenging condition for island detection. Three common, commercially available single-phase PV inverters from three different manufacturers were tested. The first part of this work examined each inverter individually using a series of pure hardware resistive-inductive-capacitive (RLC) resonant load based anti-islanding tests to determine the worst-case configuration of grid support functions for each inverter. A grid support function is a function an inverter performs to help stabilize the grid or drive the grid back towards its nominal operating point. The four grid support functions examined here were voltage ride-through, frequency ride-through, Volt-VAr control, and frequency-Watt control. The worst-case grid support configuration was defined as the configuration that led to the maximum island duration (or run-on time, ROT) out of 50 tests of each inverter. For each of the three inverters, it was observed that maximum ROT increased when voltage and frequency ride-through were activated. No conclusive evidence was found that Volt-VAr control or frequency-Watt control increased maximum ROT. Over all single-inverter test cases, the maximum ROT was 711 ms, well below the two-second limit currently imposed by IEEE Standard 1547-2003. A subsequent series of 244 experiments tested all three inverters simultaneously in the same island. These tests again used a procedure based on the IEEE 1547.1 unintentional islanding test to create a difficult-to-detect island condition. For these tests, which used the two worst-case grid support function configurations from the single-inverter tests, the inverters were connected to a variety of island circuit topologies designed to represent the variety of multiple-inverter islands that may occur on real distribution circuits. The interconnecting circuits and the resonant island load itself were represented in the real-time PHIL model. PHIL techniques similar to those employed here have been previously used and validated for anti-islanding tests, and the PHIL resonant load model used in this test was successfully validated by comparing single-inverter PHIL tests to conventional tests using an RLC load bank.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Arctic Shrub Expansion, Plant Functional Trait Variation, and Effects on Belowground Carbon Cycling (Final Technical Report)

Terrestrial ecosystems are undergoing dramatic changes in response to climate warming, and these changes are expected to feedback to the atmosphere, potentially altering the trajectory of future climate change. Feedbacks from Arctic ecosystems are a major concern because the Arctic is projected to warm significantly in the 21 st century and because >50% of global belowground organic carbon is stored in permafrost and overlying soils. Warming-driven release of this carbon could drastically increase atmospheric greenhouse gas concentrations and accelerate climate warming. Plant communities are also responding to warming, as evidenced by the widely documented increase in woody-shrub growth and “greening” across much of the Arctic tundra biome. This vegetation shift may offset or amplify warming by altering carbon cycling. The direction and magnitude of shrub effects remain highly uncertain, however, due to limited understanding of the consequences of shrub expansion for belowground carbon cycling and simplification of these relationships in models. The major shrubs expanding in the Arctic (Betula, Salix, and Alnus) vary widely with respect to aboveground and belowground traits (e.g., tissue production and chemistry, rooting depth, microbial symbionts), and may also exhibit substantial intraspecific variation in these traits in response to environmental conditions. Such variation is likely to have profound implications for soil carbon cycling. The overarching goal of this project was to improve process-based understanding of the influence of shrub expansion on carbon cycling to enable improved representation of carbon dynamics in ecosystem and Earth system models. We investigated how plant functional traits vary among shrub genera, respond to environmental conditions, and affect belowground carbon and nutrient cycling by quantifying relationships among functional traits and biogeochemical cycling along edaphic gradients nested within a climate gradient in the Alaskan tundra. We found consistent differences in leaf and root traits among shrub genera and between shrubs and a widespread sedge species, indicating diverse nutrient acquisition strategies and belowground impacts among different arctic shrubs. We also found striking differences in trait values among individuals within the same species or genera within sites. Soil parameters were more important than climate parameters for predicting size and leaf trait variation, and root trait responses were less dependent on climate overall. For all but one root trait, including parameters representing aboveground traits improved the predictive ability of models. These results demonstrate that tundra shrub traits vary considerably at local scales and soil factors drive this variation, especially belowground. Furthermore, leveraging information about aboveground traits and soil conditions can improve predictions of how belowground traits will respond to climate change. Despite these differences, soil carbon and nitrogen pools in the active layer did not vary among plots dominated by different shrub or sedge genera. Instead, pool sizes generally decreased from warmer to colder sites, consistent with a productivity gradient. Patterns of isotopic N composition indicate that shrubs tighten nitrogen cycling via nitrogen resorption or immobilization of shrub litter. Overall, these results suggest that further identifying the specific shrub genera in the tundra landscape will ultimately provide better predictions of belowground dynamics across the changing arctic. We also performed simulation experiments with the Terrestrial Ecosystem Model (TEM) incorporated in the Predictive Ecosystem Analyzer (PEcAn) framework, treats model parameters as probability distributions, estimates parameters based on a synthesis of available field data, and then quantifies both model sensitivity and uncertainty to a given parameter or suite of parameters. We performed simulations across different types of tundra, including shrub tundra. One key finding was that both model sensitivity and uncertainty to a given parameter could vary within the same type of tundra, but in a different geographical location, such as over the climate gradient of shrub tundra described above. We organized a special session at the annual meeting of the Ecological Society of America in August 2019 to disseminate our results, refine recommendations for model improvement, and initiate collaborations to implement these recommendations in existing models of tundra carbon dynamics at ecosystem to Earth system scales. Our results support DOE near-term priorities by providing mechanistic insights into the role of vegetation change in the terrestrial carbon cycle in a region that is inadequately represented in Earth system models. Current models reduce the complexity of Arctic vegetation to a small number of plant functional types (PFTs). This approach implicitly assumes that each PFT represents the average ecological function of its constituent species, thus ignoring the effects of trait variation on biogeochemical cycling and potentially leading to large uncertainty in the sign and magnitude of ecosystem feedbacks to climate. By quantifying variation of plant functional traits across broad gradients of climatic and edaphic conditions and elucidating the linkages of such variation with carbon and nutrient cycling, our results illustrate the need and create a foundation for further developing trait-based modeling approaches that allow the traits of PFTs to vary as a function of environmental conditions. These approaches should improve the capacity of simulation models to offer insights into ecosystem carbon dynamics associated with novel plant communities in a rapidly changing Arctic.

54 ENVIRONMENTAL SCIENCES↗

Beyond sequence similarity: toward function-based screening of nucleic acid synthesis

Synthetic nucleic acids are a key input to modern biotechnology, yet they represent dual-use materials that require robust screening to mitigate biosecurity risks. The prevailing screening paradigm, which identifies sequences of concern (SoCs) through sequence similarity to controlled pathogens and toxins, may not fully capture risks posed by AI tools that can decouple biomolecular function from reliance on known sequences. Rapidly advancing biodesign capabilities enable the generation of genes and proteins that might evade sequence-based detection. We highlight the critical need for function-based screening approaches that can detect sequences capable of hazardous biological functions, regardless of similarity to known SoCs. We examine the feasibility of function-based screening with an initial focus on proteins, arguing that, while protein sequence space is vast, biologically functional proteins are significantly constrained by biophysical and biochemical requirements that can be learned and modeled. We propose a concrete implementation framework organized along a continuum of complexity, starting with toxins as the most tractable targets before expanding to more complex pathogenic functions. We then discuss open challenges and describe a research and development strategy to address them.

59 BASIC BIOLOGICAL SCIENCES↗

Riverine organic matter functional diversity increases with catchment size

A large amount of dissolved organic matter (DOM) is transported to the ocean from terrestrial inputs each year (~0.95 Pg C per year) and undergoes a series of abiotic and biotic reactions, causing a significant release of CO 2 . Combined, these reactions result in variable DOM characteristics (e.g., nominal oxidation state of carbon, double-bond equivalents, chemodiversity) which have demonstrated impacts on biogeochemistry and ecosystem function. Despite this importance, however, comparatively few studies focus on the drivers for DOM chemodiversity along a riverine continuum. Here, we characterized DOM within samples collected from a stream network in the Yakima River Basin using ultrahigh-resolution mass spectrometry (i.e., FTICR-MS). To link DOM chemistry to potential function, we identified putative biochemical transformations within each sample. We also used various molecular characteristics (e.g., thermodynamic favorability, degradability) to calculate a series of functional diversity metrics. We observed that the diversity of biochemical transformations increased with increasing upstream catchment area and landcover. This increase was also connected to expanding functional diversity of the molecular formula. This pattern suggests that as molecular formulas become more diverse in thermodynamics or degradability, there is increased opportunity for biochemical transformations, potentially creating a self-reinforcing cycle where transformations in turn increase diversity and diversity increase transformations. We also observed that these patterns are, in part, connected to landcover whereby the occurrence of many landcover types (e.g., agriculture, urban, forest, shrub) could expand DOM functional diversity. For example, we observed that a novel functional diversity metric measuring similarity to common freshwater molecular formulas (i.e., carboxyl-rich alicyclic molecules) was significantly related to urban coverage. These results show that DOM diversity does not decrease along stream networks, as predicted by a common conceptual model known as the River Continuum Concept, but rather are influenced by the thermodynamic and degradation potential of molecular formula within the DOM, as well as landcover patterns.

54 ENVIRONMENTAL SCIENCES↗

The Significance of Aggregation Methods in Functional Group Modeling

The growth of forests and the feedbacks between forests and environmental changes are central issues in the planetary carbon cycle, global climate change, and basic plant ecology. A challenge to understanding both growth and feedbacks from local to global scales is that many critical metabolic processes vary among species. An innovation in solving this challenge is the recognition that species can be lumped into “functional groups” based on metabolic similarity, and these functional groups can then be studied in computational models that simulate ecosystem function. Despite the vast resources devoted to functional group studies and the progress made by them, an important logical and biological question has not been formally addressed, “How do the groupings alter the results of modeling studies?” To what extent do modeling results depend on the choices made in aggregating taxa into functional groups. Here, we consider the effects of using different aggregation strategies in simulating the carbon dynamics of a deciduous forest. Understanding the impacts that aggregation strategy has on efforts to simulate regional-to-global-scale forest dynamics offers insights into both ecosystem regulation and model function and addresses this central problem in the study of carbon dynamics.

54 ENVIRONMENTAL SCIENCES↗

Ionizing Radiation Sensing with Functionalized and Copper-Coated SWCNT/PMMA Thin Film Nanocomposites

This paper studies the ionizing radiation effects on functionalized single-walled carbon nanotube (SWCNT)/poly(methyl methacrylate) (PMMA) thin-film nanocomposites [SWNT/PMMA]. The functionalized thin-film devices are made of ferrocene-doped SWCNTs, SWCNTs functionalized with carboxylic acid (COOH), and SWCNTs coated/ modified with copper. The nanocomposite was synthesized by the solution blending method and the resulting nanocomposite was spin-cast on interdigitated electrodes (IDEs). A 160 kV X-ray source was used to irradiate the thin film and changes in the electrical resistance of the nanocomposites due to X-rays were measured using a semiconductor device analyzer. Carboxylic acid functionalized and copper-coated SWCNT/PMMA nanocomposite showed a reduced response to X-rays compared to unfunctionalized SWCNT/PMMA nanocomposite. Ferrocene-doped SWCNT showed a higher sensitivity to X-rays at lower dose rates. This is in contrast to a previous study that showed that similar nanocomposites using functionalized multi-walled CNTs (MWCNTs) had demonstrated an improved response to X-rays ionizing radiation compared to unfunctionalized MWCNTs for all dose rates. Electrical measurements were also performed using the Arduino Nano microcontroller. The result showed that a relatively economical, lightweight-designed prototype radiation sensor based on SWCNT/PMMA thin-film devices could be produced by interfacing the devices with a modest microcontroller. This work also shows that by encapsulating the SWCNT/PMMA thin-film device in a plastic container, the effect of ambient humidity can be reduced and the device can still be used to detect X-ray radiation. This study further shows that the sensitivity of SWCNT to X-rays was dependent on both the functionalization of the SWCNT and the dose rate.

36 MATERIALS SCIENCE↗

Charmonium spectral functions with the variational method in zero and finite temperature lattice QCD

We propose a method to evaluate spectral functions on the lattice based on a variational method. On a lattice with a finite spatial extent, spectral functions consist of discrete spectra only. Adopting a variational method, we calculate the locations and the heights of spectral functions at low-lying discrete spectra. We first test the method in the case of analytically solvable free Wilson quarks at zero and finite temperatures and confirm that the method well reproduces the analytic results for low-lying spectra. We find that we can systematically improve the results by increasing the number of trial states. We then apply the method to calculate the charmonium spectral functions for S and P-wave states at zero-temperature in quenched QCD and compare the results with those obtained using the conventional maximum entropy method (MEM). The results for the ground state are consistent with the location and the area of the first peak in spectral functions from the MEM, while the variational method leads to a mass which is closer to the experimental value for the first excited state. We also investigate the temperature dependence of the spectral functions for S-wave states below and above T{sub c}. We obtain no clear evidences for dissociation of J/{psi} and {eta}{sub c} up to 1.4 T{sub c}.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Direct SN Treatment of the Scattering Source with Phase Functions

In deterministic transport, the scattering operator is commonly expressed using a spherical harmonics (pn) expansion of the scattering source. Not only does this require minimal modifications if the problem dimensionality is changed, but it also contains little to no approximation whenever the scattering anisotropy degree is small. An alternative method relying on a discrete ordinates (sn) approach -- essentially computing the angular integral of the phase function with a finite number of weighted directions -- is theoretically possible and has shown some advantages. In particular, this method was introduced for neutron elastic scattering and was shown to be more accurate for highly anisotropic group-to-group transfer cross-sections. Benefits were further shown in the case of a collimated beam in highly forward peaked scattering media, particularly reducing the memory usage by storing an angle-to-angle collision matrix rather than a large number of angular moments. In addition, the scattering source was expressed using that same method, the phase function having been previously expanded using Legendre polynomials, in the context of achieving extreme precision while solving the 1D radiative transfer equation. Based on these previous works, we aim at exploring two questions. First, we wish to derive an expression of the phase function in reduced geometries that does not require any more angular quadrature points than for a standard sn calculation. This is particularly relevant in 2-D problems where the reduced phase function does not solely depend on the product of the incoming and outgoing directions. Second, we wish to better understand the relationship between the sn and pn treatments. We in particular show equivalence if the phase function in the former case is expanded Legendre polynomials. This equivalence is verified numerically and the computational costs of the methods are compared on a test problem involving a Dirac delta phase function.

97 MATHEMATICS AND COMPUTING↗

A regulatory perspective on the response function method for determining allowable content of a radioactive materials transportation package or storage cask - 15023

In order to simplify shielding design, there has been an increasingly use of a so-called dose rate response function method for determining the allowable contents in radioactive materials (including spent fuel) transportation package and spent fuel storage cask designs. In essence, this approach uses a pre-calculated dose rate at a given location outside the storage cask or transportation package for a given source inside the cask. It assumes that there is a one-to-one relationship between a source inside the cask and the dose rate outside the cask, i.e., a dose rate response function of a source. Thus, the allowable content is obtained by simply dividing the targeted dose rate by the response function. This method converts the complex particle transport problem into a simple arithmetic calculation. If used correctly and prudently, this approach can greatly simplify the shielding design of casks. However, the use of this method must demonstrate the validity of the assumption, that is, the nuclear physics property of the media through which the particle transverses must be similar to that used in computing the response function. Because of the assumptions and approximations, either implicitly or explicitly, made in the models for dose rate response functions, to assure safety the users should also consider the errors in the models and the bias and uncertainties associated with the code used to calculate the response function. This paper reviewed the advantages and some of the major potential pitfalls of this method from the regulatory perspective. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Green’s Function Perspective on the Nonlinear Density Response of Quantum Many-Body Systems

We derive equations of motion for higher order density response functions using the theory of thermodynamic Green’s functions. We also derive expressions for the higher order generalized dielectric functions and polarization functions. Moreover, we relate higher order response functions and higher order collision integrals within the Martin–Schwinger hierarchy. We expect our results to be highly relevant to the study of a variety of quantum many-body systems such as matter under extreme temperatures, densities, and pressures.

Density Functional Theory↗

Recent progress on nuclear parton distribution functions

We report current status of global analyses on nuclear parton distribution functions (NPDFs). The optimum NPDFs are determined by analyzing high-energy nuclear reaction data. Due to limited experimental measurements, antiquark modifications have large uncertainties at x > 0.2 and gluon modifications cannot be determined. A nuclear modification difference between u and d quark distributions could be an origin of the long-standing NuTeV sin{sup 2}{theta}{sub w} anomaly. There is also an issue of nuclear modification differences between the structure functions of charged-lepton and neutrino reactions. Next, nuclear clustering effects are discussed in structure functions F{sub 2}{sup A} as a possible explanation for an anomalous result in the {sup 9}Be nucleus at the Thomas Jefferson National Accelerator Facility (JLab). Last, tensor-polarized quark and antiquark distribution functions are extracted from HERMES data on the polarized structure function b{sub 1} of the deuteron, and they could be used for testing theoretical models and for proposing future experiments, for example, the one at JLab. Such measurements could open a new field of spin physics in spin-one hadrons.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Long-range correlation energy calculated from coupled atomic response functions

An accurate determination of the electron correlation energy is an essential prerequisite for describing the structure, stability, and function in a wide variety of systems. Therefore, the development of efficient approaches for the calculation of the correlation energy (and hence the dispersion energy as well) is essential and such methods can be coupled with many density-functional approximations, local methods for the electron correlation energy, and even interatomic force fields. In this work, we build upon the previously developed many-body dispersion (MBD) framework, which is intimately linked to the random-phase approximation for the correlation energy. We separate the correlation energy into short-range contributions that are modeled by semi-local functionals and long-range contributions that are calculated by mapping the complex all-electron problem onto a set of atomic response functions coupled in the dipole approximation. We propose an effective range-separation of the coupling between the atomic response functions that extends the already broad applicability of the MBD method to non-metallic materials with highly anisotropic responses, such as layered nanostructures. Application to a variety of high-quality benchmark datasets illustrates the accuracy and applicability of the improved MBD approach, which offers the prospect of first-principles modeling of large structurally complex systems with an accurate description of the long-range correlation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy density functionals from the strong-coupling limit applied to the anions of the He isoelectronic series

Anions and radicals are important for many applications including environmental chemistry, semiconductors, and charge transfer, but are poorly described by the available approximate energy density functionals. Here we test an approximate exchange-correlation functional based on the exact strong-coupling limit of the Hohenberg-Kohn functional on the prototypical case of the He isoelectronic series with varying nuclear charge Z < 2, which includes weakly bound negative ions and a quantum phase transition at a critical value of Z, representing a big challenge for density functional theory. We use accurate wavefunction calculations to validate our results, comparing energies and Kohn-Sham potentials, thus also providing useful reference data close to and at the quantum phase transition. We show that our functional is able to bind H{sup −} and to capture in general the physics of loosely bound anions, with a tendency to strongly overbind that can be proven mathematically. We also include corrections based on the uniform electron gas which improve the results.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Density functional theory and chromium: Insights from the dimers

The binding in small Cr clusters is re-investigated, where the correct description of the dimer in three charge states is used as criterion to assign the most suitable density functional theory approximation. The difficulty in chromium arises from the subtle interplay between energy gain from hybridization and energetic cost due to exchange between s and d based molecular orbitals. Variations in published bond lengths and binding energies are shown to arise from insufficient numerical representation of electron density and Kohn-Sham wave-functions. The best functional performance is found for gradient corrected (GGA) functionals and meta-GGAs, where we find severe differences between functionals from the same family due to the importance of exchange. Only the “best fit” from Bayesian error estimation is able to predict the correct energetics for all three charge states unambiguously. With this knowledge, we predict small bond-lengths to be exclusively present in Cr{sub 2} and Cr{sub 2}{sup −}. Already for the dimer cation, solely long bond-lengths appear, similar to what is found in the trimer and in chromium bulk.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗