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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 1,351 records · Page 75
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

A remarkable case of basis set dependence: the false convergence patterns of the methyl anion

Here, the gas phase methyl anion, CH 3 ¯, has been difficult to study experimentally, and the extreme basis set dependence of its molecular properties has presented a comparable challenge to theoreticians. Reliable predictions for the electronic structure of CH 3 ¯ require the use of basis sets capable of describing both the diffuse and valence characteristics of the system. The present study examines the basis set dependence of the equilibrium geometry and harmonic vibrational frequencies of CH 3 ¯. Both Hartree–Fock and CCSD(T) levels of theories are used with cc-pVXZ (, T, Q, 5, 6) basis sets with up to triple augmentation to describe the diffuse nature of the electron distribution. We find that non-augmented basis sets systematically yield vibrational frequencies that are too high for the umbrella mode and too low for the C–H symmetric and antisymmetric stretch even when extrapolated to the complete basis set limit, displaying false convergence patterns. The inclusion of one set of augmented functions significantly improves the convergence of these properties, but again yields false convergence patterns. Only with the doubly augmented basis set do we approach the basis set limit for the CH 3 ¯ vibrational frequencies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2011

Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark

Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and 3 transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 x 10{sup 4} deg cm{sup 2} dmol{sup -1}. The performance of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LR-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LR-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Affordable and accurate large-scale hybrid-functional calculations on GPU-accelerated supercomputers

Performing high accuracy hybrid functional calculations for condensed matter systems containing a large number of atoms is at present computationally very demanding or even out of reach if high quality basis sets are used. We present a highly optimized multiple graphics processing unit implementation of the exact exchange operator which allows one to perform fast hybrid functional density-functional theory (DFT) calculations with systematic basis sets without additional approximations for up to a thousand atoms. With this method hybrid DFT calculations of high quality become accessible on state-of-the-art supercomputers within a time-to-solution that is of the same order of magnitude as traditional semilocal-GGA functionals. The method is implemented in a portable open-source library.

density functional theory↗
DOE OSTI2016

A rank-exploiting infinite Arnoldi algorithm for nonlinear eigenvalue problems

We consider the nonlinear eigenvalue problem M ( λ ) x = 0, where M ( λ ) is a large parameter-dependent matrix. In several applications, M ( λ ) has a structure where the higher-order terms of its Taylor expansion have a particular low-rank structure. We propose a new Arnoldi-based algorithm that can exploit this structure. More precisely, the proposed algorithm is equivalent to Arnoldi's method applied to an operator whose reciprocal eigenvalues are solutions to the nonlinear eigenvalue problem. The iterates in the algorithm are functions represented in a particular structured vector-valued polynomial basis similar to the construction in the infinite Arnoldi method [Jarlebring, Michiels, and Meerbergen, Numer. Math., 122 (2012), pp. 169–195]. In this paper, the low-rank structure is exploited by applying an additional operator and by using a more compact representation of the functions. This reduces the computational cost associated with orthogonalization, as well as the required memory resources. The structure exploitation also provides a natural way in carrying out implicit restarting and locking without the need to impose structure in every restart. In conclusion, the efficiency and properties of the algorithm are illustrated with two large-scale problems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry

Static polarizabilities are the first response of the electron density to electric fields, and are therefore important for predicting intermolecular and molecule-field interactions. They also offer a global measure of the accuracy of the treatment of excited states by density functionals in a formally exact manner. We have developed a database of benchmark static polarizabilities for 132 small species at equilibrium geometry, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals. The performance of 60 popular and recent functionals are also assessed, which indicates that double hybrid functionals perform the best, having RMS relative errors in the range of 2.5-3.8%. Many hybrid functionals also give quite reasonable estimates with 4-5% RMS relative error. A few meta-GGAs like mBEEF and MVS yield performance comparable to hybrids, indicating potential for improved excited state predictions relative to typical local functionals. Some recent functionals however are found to be prone to catastrophic failure (possibly as a consequence of overparameterization), indicating a need for caution in applying these.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Soil enzymes as indicators of soil function: A step toward greater realism in microbial ecological modeling

Soil carbon (C) and nitrogen (N) cycles and their complex responses to environmental changes have received increasing attention. However, large uncertainties in model predictions remain, partially due to the lack of explicit representation and parameterization of microbial processes. One great challenge is to effectively integrate rich microbial functional traits into ecosystem modeling for better predictions. Here, using soil enzymes as indicators of soil function, we developed a competitive dynamic enzyme allocation scheme and detailed enzyme-mediated soil inorganic N processes in the Microbial-ENzyme Decomposition (MEND) model. We conducted a rigorous calibration and validation of MEND with diverse soil C-N fluxes, microbial C:N ratios, and functional gene abundances from a 12-year CO 2 × N grassland experiment (BioCON) in Minnesota, USA. In addition to accurately simulating soil CO 2 fluxes and multiple N variables, the model correctly predicted microbial C:N ratios and their negative response to enriched N supply. Model validation further showed that, compared to the changes in simulated enzyme concentrations and decomposition rates, the changes in simulated activities of eight C-N-associated enzymes were better explained by the measured gene abundances in responses to elevated atmospheric CO 2 concentration. In conclusion, our results demonstrated that using enzymes as indicators of soil function and validating model predictions with functional gene abundances in ecosystem modeling can provide a basis for testing hypotheses about microbially mediated biogeochemical processes in response to environmental changes. Further development and applications of the modeling framework presented here will enable microbial ecologists to address ecosystem-level questions beyond empirical observations, toward more predictive understanding, an ultimate goal of microbial ecology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

AP1000{sup R} design robustness against extreme external events - Seismic, flooding, and aircraft crash

Both the International Atomic Energy Agency (IAEA) and the U.S. Nuclear Regulatory Commission (NRC) require existing and new nuclear power plants to conduct plant assessments to demonstrate the unit's ability to withstand external hazards. The events that occurred at the Fukushima-Dai-ichi nuclear power station demonstrated the importance of designing a nuclear power plant with the ability to protect the plant against extreme external hazards. The innovative design of the AP1000{sup R} nuclear power plant provides unparalleled protection against catastrophic external events which can lead to extensive infrastructure damage and place the plant in an extended abnormal situation. The AP1000 plant is an 1100-MWe pressurized water reactor with passive safety features and extensive plant simplifications that enhance construction, operation, maintenance and safety. The plant's compact safety related footprint and protection provided by its robust nuclear island structures prevent significant damage to systems, structures, and components required to safely shutdown the plant and maintain core and spent fuel pool cooling and containment integrity following extreme external events. The AP1000 nuclear power plant has been extensively analyzed and reviewed to demonstrate that it's nuclear island design and plant layout provide protection against both design basis and extreme beyond design basis external hazards such as extreme seismic events, external flooding that exceeds the maximum probable flood limit, and malicious aircraft impact. The AP1000 nuclear power plant uses fail safe passive features to mitigate design basis accidents. The passive safety systems are designed to function without safety-grade support systems (such as AC power, component cooling water, service water, compressed air or HVAC). The plant has been designed to protect systems, structures, and components critical to placing the reactor in a safe shutdown condition within the steel containment vessel which is further surrounded by a substantial 'steel concrete' composite shield building. The containment vessel is not affected by external flooding, and the shield building design provides hazard protection beyond that provided by a comparable reinforced concrete structure. The intent of this paper is to demonstrate the robustness of the AP1000 design against extreme events. The paper will focus on the plants ability to withstand extreme external events such as beyond design basis flooding, seismic events, and malicious aircraft impact. The paper will highlight the robustness of the AP1000 nuclear island design including the protection provided by the unique AP1000 composite shield building. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2014

Dispersion of the linear and nonlinear optical susceptibilities of the CuAl(S{sub 1–x}Se{sub x})₂ mixed chaclcopyrite compounds

Based on the electronic band structure, we have calculated the dispersion of the linear and nonlinear optical susceptibilities for the mixed CuAl(S{sub 1–x}Se{sub x})₂ chaclcopyrite compounds with x=0.0, 0.25, 0.5, 0.75, and 1.0. Calculations are performed within the Perdew-Becke-Ernzerhof general gradient approximation. The investigated compounds possess a direct band gap of about 2.2 eV (CuAlS₂), 1.9 eV (CuAl(S₀.₇₅Se₀.₂₅)₂), 1.7 eV (CuAl(S₀.₅Se₀.₅)₂), 1.5 eV (CuAl(S₀.₂₅Se₀.₇₅)₂), and 1.4 eV (CuAlSe₂) which tuned to make them optically active for the optoelectronics and photovoltaic applications. These results confirm that substituting S by Se causes significant band gaps' reduction. The optical function's dispersion ε₂{sup xx}(ω) and ε₂{sup zz}(ω)/ε₂{sup xx}(ω), ε₂{sup yy}(ω), and ε₂{sup zz}(ω) was calculated and discussed in detail. To demonstrate the effect of substituting S by Se on the complex second-order nonlinear optical susceptibility tensors, we performed detailed calculations for the complex second-order nonlinear optical susceptibility tensors, which show that the neat parents compounds CuAlS₂ and CuAlSe₂ exhibit | χ₁₂₂²}(-2ω;ω;ω) | as the dominant component, while the mixed alloys exhibit | χ₁₁₁²(-2ω;ω;ω) | as the dominant component. The features of | χ₁₂₃²}(-2ω;ω;ω) | and | χ{sub 111}²}(-2ω;ω;ω) | spectra were analyzed on the basis of the absorptive part of the corresponding dielectric function ε₂(ω) as a function of both ω/2 and ω.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Supercritical fluids behave as complex networks

Abstract Supercritical fluids play a key role in environmental, geological, and celestial processes, and are of great importance to many scientific and engineering applications. They exhibit strong variations in thermodynamic response functions, which has been hypothesized to stem from the microstructural behavior. However, a direct connection between thermodynamic conditions and the microstructural behavior, as described by molecular clusters, remains an outstanding issue. By utilizing a first-principles-based criterion and self-similarity analysis, we identify energetically localized molecular clusters whose size distribution and connectivity exhibit self-similarity in the extended supercritical phase space. We show that the structural response of these clusters follows a complex network behavior whose dynamics arises from the energetics of isotropic molecular interactions. Furthermore, we demonstrate that a hidden variable network model can accurately describe the structural and dynamical response of supercritical fluids. These results highlight the need for constitutive models and provide a basis to relate the fluid microstructure to thermodynamic response functions.

42 ENGINEERING↗
DOE OSTI2011

RECONSTRUCTION OF LONG-LIVED RADIONUCLIDE INTAKES FOR TECHA RIVERSIDE RESIDENTS: STRONTIUM-90

Releases of radioactive materials from the Mayak Production Association in 1949-1956 resulted in contamination of the Techa River; a nuclide of major interest was 90Sr, which downstream residents consumed with water from the river and with milk contaminated by cow's consumption of river water and contaminated pasture. Over the years, several reconstructions of dose have been performed for the approximately 30,000 persons who make up the Extended Techa River Cohort. The purpose of the study described here was to derive a revised reference-90Sr-intake function for the members of this cohort. The revision was necessary because recently discovered data have provided a more accurate description of the time course of the releases, and more is now known about the importance of the pasture grass-cow-milk pathway for the members of this cohort. The fundamental basis for the derivation of the reference-90Sr-intake function remains the same: thousands of measurements of 90Sr content in bone with a special whole-body counter, thousands of measurement of beta-activity of front teeth with a special tooth-beta counter, and a variety of other measurements, including post mortem measurements of 90Sr in bone, measurements of 90Sr in cow's milk, and measurements of beta activity in human excreta. Results of the new analyses are that the major intake started in September 1950 and peaked somewhat later than originally postulated. However, the total intake for adult residents has not changed significantly. For children of some birth years, the intake and incorporation of 90Sr in bone tissue have changed substantially.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2016

A facile approach towards synthesis, characterization, single crystal structure, and DFT study of 5-bromosalicylalcohol

5-Bromosalicylalcohol was prepared by the interaction of NaBH{sub 4} and 5-bromosalicylaldehyde. The use of sodium borohydride makes the reaction easy, facile, economic and does not require any toxic catalyst. The compound is characterized by FTIR, {sup 1}H NMR, {sup 13}C NMR, TEM and ESI-mass spectra. Crystal structure is determined by single crystal X-ray analysis. Quantum mechanical calculations of geometries, energies and thermodynamic parameters are carried out using density functional theory (DFT/B3LYP) method with 6-311G(d,p) basis set. The optimized geometrical parameters obtained by B3LYP method show good agreement with experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Single-Point Extrapolation to the Complete Basis Set Limit through Deep Learning

Machine learning (ML) offers an attractive method for making predictions about molecular systems while circumventing the need to run expensive electronic structure calculations. Once trained on ab initio data, the promise of ML is to deliver accurate predictions of molecular properties that were previously computationally infeasible. In this work, we develop and train a graph neural network model to correct the basis set incompleteness error (BSIE) between a small and large basis set at the RHF and B3LYP levels of theory. Our results show that, when compared to fitting to the total potential, an ML model fitted to correct the BSIE is better at generalizing to systems not seen during training. We test this ability by training on single molecules while evaluating on molecular complexes. We also show that ensemble models yield better behaved potentials in situations where the training data is insufficient. However, even when only fitting to the BSIE, acceptable performance is only achieved when the training data sufficiently resemble the systems one wants to make predictions on. As a result, the test error of the final model trained to predict the difference between the cc-pVDZ and cc-pV5Z potential is 0.184 kcal/mol for the B3LYP density functional, and the ensemble model accurately reproduces the large basis set interaction energy curves on the S66x8 dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

A theoretical study on 3-(4-methoxyphenyl)-1-(pyridin-2-Yl) prop-2-en-1-one

This study reports the geometric parameters, vibration frequencies, {sup 13}C and {sup 1}H NMR chemical shifts of 3-(4-Methoxyphenyl)-1-(pyridin-2-yl) prop-2-en-1-one (MPP) molecule calculated by B3LYP level of density functional theory (DFT) with 6-311++G(d,p) basis set. {sup 13}C and {sup 1}H NMR chemical shifts were calculated within GIAO approach which is one of the most common approaches. Additionally, 3D molecular surfaces such as molecular electrostatic potential (MEP) and electrostatic potential (ESP), were simulated by the same level. As a result, obtained theoretical results were found to be consistent with experimental ones. All of calculations were carried out Gaussian 09 package program.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

Long-term Performance of Engineered Barrier Systems (PEBS) - An International EURATOM Project on the Study and Testing of Engineered Barriers for the Final Disposal of HAW Using PEBS as an Example - 13299

The main aim of the PEBS project is to evaluate the sealing and barrier performance of the EBS over time, through development of a comprehensive approach involving experiments, model development, and consideration of the potential impacts on long-term safety functions. The experiments and models cover the full range of conditions, from initial emplacement of wastes (high heat generation and EBS re-saturation) through to later stage establishment of near steady state conditions, i.e. full re-saturation and thermal equilibrium with the host rock. These aspects will be integrated in a manner that will lead to greater certainty and thus greater confidence regarding the development from the initial transient state of the EBS to its long-term state, which provides the required isolation of the wastes. The work proposed within the project builds on existing knowledge and experience generated during recent years and supported by ongoing national and EC research programs. The project aims to provide a more complete description of the THM and THMC (thermo-hydro-mechanical- chemical) evolution of the EBS system, a more quantitative basis for relating the evolutionary behavior to the safety functions of the system, and a further clarification of the significance of residual uncertainties for long-term performance assessment. The importance of uncertainties arising from potential disagreement between the process models and the laboratory and in-situ experiments to be performed within PEBS, and their implications for an extrapolation of the results, will be reviewed, with particular emphasis on possible impacts on safety functions. In addition to the scientific-technical aims, the consortium will disseminate the basic findings to the broad scientific community within the EU, China and Japan, use expertise gained for public information purposes, and promote knowledge and technology transfer through training. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Structural Basis of Substrate Specificity and Regiochemistry in the MycF/TylF Family of Sugar O -Methyltransferases.

Sugar moieties in natural products are frequently modified by O-methylation. In the biosynthesis of the macrolide antibiotic mycinamicin, methylation of a 6'-deoxyallose substituent occurs in a stepwise manner first at the 2'- and then the 3'-hydroxyl groups to produce the mycinose moiety in the final product. The timing and placement of the O-methylations impact final stage C-H functionalization reactions mediated by the P450 monooxygenase MycG. The structural basis of pathway ordering and substrate specificity is unknown. A series of crystal structures of MycF, the 3'-O-methyltransferase, including the free enzyme and complexes with S-adenosyl homocysteine (SAH), substrate, product, and unnatural substrates, show that SAM binding induces substantial ordering that creates the binding site for the natural substrate, and a bound metal ion positions the substrate for catalysis. A single amino acid substitution relaxed the 2'-methoxy specificity but retained regiospecificity. The engineered variant produced a new mycinamicin analog, demonstrating the utility of structural information to facilitate bioengineering approaches for the chemoenzymatic synthesis of complex small molecules containing modified sugars. Using the MycF substrate complex and the modeled substrate complex of a 4'-specific homolog, active site residues were identified that correlate with the 3'- or 4'- specificity of MycF family members and define the protein and substrate features that direct the regiochemistry of methyltransfer. Lastly, this classification scheme will be useful in the annotation of new secondary metabolite pathways that utilize this family of enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗