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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Nonlinear electronic excitations in crystalline solids using meta-generalized gradient approximation and hybrid functional in time-dependent density functional theory

We develop methods to calculate electron dynamics in crystalline solids in real-time time-dependent density functional theory employing exchange-correlation potentials which reproduce band gap energies of dielectrics; a meta-generalized gradient approximation was proposed by Tran and Blaha [Phys. Rev. Lett. 102, 226401 (2009)] (TBm-BJ) and a hybrid functional was proposed by Heyd, Scuseria, and Ernzerhof [J. Chem. Phys. 118, 8207 (2003)] (HSE). In time evolution calculations employing the TB-mBJ potential, we have found it necessary to adopt the predictor-corrector step for a stable time evolution. We have developed a method to evaluate electronic excitation energy without referring to the energy functional which is unknown for the TB-mBJ potential. For the HSE functional, we have developed a method for the operation of the Fock-like term in Fourier space to facilitate efficient use of massive parallel computers equipped with graphic processing units. We compare electronic excitations in silicon and germanium induced by femtosecond laser pulses using the TB-mBJ, HSE, and a simple local density approximation (LDA). At low laser intensities, electronic excitations are found to be sensitive to the band gap energy: they are close to each other using TB-mBJ and HSE and are much smaller in LDA. At high laser intensities close to the damage threshold, electronic excitation energies do not differ much among the three cases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Assessment of strontium oxide functionalized graphene nanoflakes for enhanced photocatalytic activity: A density functional theory approach

A series of strontium oxide functionalized graphene nanoflakes were designed and their optoelectronic properties were studied for enhanced photocatalytic activity. The efficiency of designed molecules was studied using various parameters such as HOMO-LUMO energy gap, light harvesting efficiency and exciton binding energy. The computed results show that by increasing the degree of functionalization of strontium oxide leads to lowering the band gap of hydrogen terminated graphene nanoflakes. Furthermore, the study explores the role of strontium oxide functionalization in Frontier Molecular Orbitals, ionization potential, electron affinity, exciton binding energy and light harvesting efficiency of designed molecules. The infrared and Raman spectra were simulated for pure and SrO functionalized graphene nanoflakes. The electron rich and electron deficient regions which are favorable for electrophilic and nucleophilic attacks respectively were analyzed using molecular electrostatic potential surface analysis.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen’s pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

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

Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

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

The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory

This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other properties such as geometries, reaction barrier heights, and atomization energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

THE PANCHROMATIC HUBBLE ANDROMEDA TREASURY. IV. A PROBABILISTIC APPROACH TO INFERRING THE HIGH-MASS STELLAR INITIAL MASS FUNCTION AND OTHER POWER-LAW FUNCTIONS

We present a probabilistic approach for inferring the parameters of the present-day power-law stellar mass function (MF) of a resolved young star cluster. This technique (1) fully exploits the information content of a given data set; (2) can account for observational uncertainties in a straightforward way; (3) assigns meaningful uncertainties to the inferred parameters; (4) avoids the pitfalls associated with binning data; and (5) can be applied to virtually any resolved young cluster, laying the groundwork for a systematic study of the high-mass stellar MF (M {approx}> 1 M {sub Sun }). Using simulated clusters and Markov Chain Monte Carlo sampling of the probability distribution functions, we show that estimates of the MF slope, {alpha}, are unbiased and that the uncertainty, {Delta}{alpha}, depends primarily on the number of observed stars and on the range of stellar masses they span, assuming that the uncertainties on individual masses and the completeness are both well characterized. Using idealized mock data, we compute the theoretical precision, i.e., lower limits, on {alpha}, and provide an analytic approximation for {Delta}{alpha} as a function of the observed number of stars and mass range. Comparison with literature studies shows that {approx}3/4 of quoted uncertainties are smaller than the theoretical lower limit. By correcting these uncertainties to the theoretical lower limits, we find that the literature studies yield ({alpha}) = 2.46, with a 1{sigma} dispersion of 0.35 dex. We verify that it is impossible for a power-law MF to obtain meaningful constraints on the upper mass limit of the initial mass function, beyond the lower bound of the most massive star actually observed. We show that avoiding substantial biases in the MF slope requires (1) including the MF as a prior when deriving individual stellar mass estimates, (2) modeling the uncertainties in the individual stellar masses, and (3) fully characterizing and then explicitly modeling the completeness for stars of a given mass. The precision on MF slope recovery in this paper are lower limits, as we do not explicitly consider all possible sources of uncertainty, including dynamical effects (e.g., mass segregation), unresolved binaries, and non-coeval populations. We briefly discuss how each of these effects can be incorporated into extensions of the present framework. Finally, we emphasize that the technique and lessons learned are applicable to more general problems involving power-law fitting.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Characterizing the Lyα forest flux probability distribution function using Legendre polynomials

The Lyman-α forest is a highly non-linear field with considerable information available in the data beyond the power spectrum. The flux probability distribution function (PDF) has been used as a successful probe of small-scale physics. In this paper we argue that measuring coefficients of the Legendre polynomial expansion of the PDF offers several advantages over measuring the binned values as is commonly done. In particular, the n -th Legendre coefficient can be expressed as a linear combination of the first n moments, allowing these coefficients to be measured in the presence of noise and allowing a clear route for marginalisation over mean flux. Moreover, in the presence of noise, our numerical work shows that a finite number of coefficients are well measured with a very sharp transition into noise dominance. This compresses the available information into a small number of well-measured quantities. In conclusion, we find that the amount of recoverable information is a very non-linear function of spectral noise that strongly favors fewer quasars measured at better signal to noise.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Lattice-QCD Computable Quark Correlation Functions at Three-Loop Order and Extraction of Splitting Functions

We present the first complete next-to-next-to-next-to-leading-order calculation of the matching coefficients that link unpolarized flavor nonsinglet parton distribution functions with lattice QCD computable correlation functions. By using this high-order result, we notice a reduction in theoretical uncertainties compared to relying solely on previously known lower-order matching coefficients. Furthermore, based on this result we have extracted the three-loop unpolarized flavor nonsinglet splitting function, which is in agreement with the state-of-the-art result. Because of the simplicity of our method, it has the potential to advance the calculation of splitting functions to the desired four-loop order.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2015

Functional renormalization-group approaches, one-particle (irreducible) reducible with respect to local Green’s functions, with dynamical mean-field theory as a starting point

We consider formulations of the functional renormalization-group (fRG) flow for correlated electronic systems with the dynamical mean-field theory as a starting point. We classify the corresponding renormalization-group schemes into those neglecting one-particle irreducible six-point vertices (with respect to the local Green’s functions) and neglecting one-particle reducible six-point vertices. The former class is represented by the recently introduced DMF{sup 2}RG approach [31], but also by the scale-dependent generalization of the one-particle irreducible representation (with respect to local Green’s functions, 1PI-LGF) of the generating functional [20]. The second class is represented by the fRG flow within the dual fermion approach [16, 32]. We compare formulations of the fRG approach in each of these cases and suggest their further application to study 2D systems within the Hubbard model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Excited state electron transfer in A 2 and A 2 B 2 functionalized zinc porphyrins carrying rigid and flexible β -pyrrole π-extended substituents

Optical absorption and emission, electrochemical, and photochemical properties of peripherally functionalized with flexible and rigid π-extended substituents on A 2 and A 2 B 2 type zinc porphyrins is investigated. The significance of rigid π-substituents over flexible ones in governing the spectral properties is unraveled. Flexible π-substituents on the porphyrin ring caused appreciable spectral broadening compared to porphyrin carrying rigid π-substituents. Further, supramolecular dyads are formed by coordinating phenyl imidazole functionalized fullerene, C 60 Im. Here, the calculated binding constants for the 1:1 complexes is in the order of 2–7 × 10 5 M −1 suggesting stable complex formation. Free-energy calculations performed according to the Rehm–Weller approach suggested possibility of excited state electron transfer in these dyads. Femtosecond transient absorption studies of the dyads performed in o-dichlorobenzene showed evidence of occurrence of electron transfer from the singlet-excited state that was in competition with the intersystem crossing process to populate the triplet-excited state of porphyrins.

A2 and A2B2 functionalized zinc↗
DOE OSTI2017

The velocity distribution function of galaxy clusters as a cosmological probe

We present a new approach for quantifying the abundance of galaxy clusters and constraining cosmological parameters using dynamical measurements. In the standard method, galaxy line-of-sight velocities, v, or velocity dispersions are used to infer cluster masses, M, to quantify the halo mass function (HMF), dn(M)/dlog(M), which is strongly affected by mass measurement errors. In our new method, the probability distributions of velocities for each cluster in the sample are summed to create a new statistic called the velocity distribution function (VDF), dn(v)/dv. The VDF can be measured more directly and precisely than the HMF and can be robustly predicted with cosmological simulations that capture the dynamics of subhalos or galaxies. We apply these two methods to realistic (ideal) mock cluster catalogs with (without) interlopers and forecast the bias and constraints on the matter density parameter Ω{sub m} and the amplitude of matter fluctuations σ{sub 8} in flat ΛCDM cosmologies. For an example observation of 200 massive clusters, the VDF with (without) interloping galaxies constrains the parameter combination σ{sub 8} Ω{sub m}{sup 0.29(0.29)}=0.589±0.014 (0.584±0.011) and shows only minor bias. However, the HMF with interlopers is biased to low Ω{sub m} and high σ{sub 8} and the fiducial model lies well outside of the forecast constraints, prior to accounting for Eddington bias. When the VDF is combined with constraints from the cosmic microwave background, the degeneracy between cosmological parameters can be significantly reduced. Upcoming spectroscopic surveys that probe larger volumes and fainter magnitudes will provide clusters for applying the VDF as a cosmological probe.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Functional approach to exploring climatic and landscape controls of runoff generation: 1. Behavioral constraints on runoff volume

Abstract Inspired by the Dunne diagram, the climatic and landscape controls on the partitioning of annual runoff into its various components (Hortonian and Dunne overland flow and subsurface stormflow) are assessed quantitatively, from a purely theoretical perspective. A simple distributed hydrologic model has been built sufficient to simulate the effects of different combinations of climate, soil, and topography on the runoff generation processes. The model is driven by a sequence of simple hypothetical precipitation events, for a large combination of climate and landscape properties, and hydrologic responses at the catchment scale are obtained through aggregation of grid‐scale responses. It is found, first, that the water balance responses, including relative contributions of different runoff generation mechanisms, could be related to a small set of dimensionless similarity parameters. These capture the competition between the wetting, drying, storage, and drainage functions underlying the catchment responses, and in this way, provide a quantitative approximation of the conceptual Dunne diagram. Second, only a subset of all hypothetical catchment/climate combinations is found to be “behavioral,” in terms of falling sufficiently close to the Budyko curve, describing mean annual runoff as a function of climate aridity. Furthermore, these behavioral combinations are mostly consistent with the qualitative picture presented in the Dunne diagram, indicating clearly the commonality between the Budyko curve and the Dunne diagram. These analyses also suggest clear interrelationships amongst the “behavioral” climate, soil, and topography parameter combinations, implying these catchment properties may be constrained to be codependent in order to satisfy the Budyko curve.

Li, Hong‐Yi↗
DOE OSTI2020

Time‐Dependent Density Functional Theory of Narrow Band Gap Semiconductors Using a Screened Range‐Separated Hybrid Functional

Abstract Predicting the band structure and optical absorption spectra of narrow band gap semiconductors is challenging for electronic structure methods. Here, it is shown shown that density functional theory can yield accurate band structures and time‐dependent density functional theory (TDDFT) can yield accurate optical absorption spectra for these systems. This is achieved by using a screened range‐separated hybrid (SRSH) functional with a single empirical parameter, fit to reproduce the experimental band gap. By comparing TDDFT results based on the SRSH approach with those obtained based on the Heyd–Scuseria–Ernzerhof functional it is shown that screened long‐range exact exchange improves the accuracy of the TDDFT spectra for these systems.

Wing, Dahvyd↗
DOE OSTI2017

Highly Efficient Carbon Monoxide Capture by Carbanion-Functionalized Ionic Liquids through C-Site Interactions

A novel method for the highly efficient and reversible capture of CO in carbanion-functionalized ionic liquids (ILs) by a C-site interaction is reported. Because of its supernucleophilicity, the carbanion in ILs could absorb CO efficiently. As a result, a relatively high absorption capacity for CO (up to 0.046 mol mol -1 ) was achieved under ambient conditions, compared with CO solubility in a commonly used IL [Bmim][Tf 2 N] (2×10 -3 mol mol -1 ). The results of quantum mechanical calculations and spectroscopic investigation confirmed that the chemical interaction between the C-site in the carbanion and CO resulted in the superior CO absorption capacities. In addition, the subsequent conversion of captured CO into valuable chemicals with good reactivity was also realized through the alkoxycarbonylation reaction under mild conditions. Highly efficient CO absorption by carbanion-functionalized ILs provides a new way of separating and converting CO.

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

Leveraging Actinide Hydrolysis Chemistry for Targeted Th and U Separations using Amidoxime-Functionalized Poly(HIPE)s

Polymerized high internal phase emulsions (poly(HIPE)s) are porous polymer monoliths whose synthesis can easily be tailored to allow incorporation of functional units. In this work, nitrile containing poly(HIPE)s have been prepared with either acrylonitrile (AN) or 4-cyanostyrene (4CS) comonomers. Post-synthetic modification of these nitrile-containing poly(HIPE)s yields their corresponding amidoximated analogues, which were studied for actinide uptake. These amidoxime-functionalized, porous polymers were shown to adsorb 95 % Th4+ species from aqueous solution within 30 minutes. In contrast to other amidoxime containing polymers the uptake of UO22+ in these poly(HIPE)s is lower under similar conditions. A critical analysis of actinide separations and high-energy X-ray scattering data provides insight into the polymers’ selectivity, enabled by the uptake of multinuclear Th clusters.

actinides↗
DOE OSTI2020

The tensor t‐function: A definition for functions of third‐order tensors

Summary A definition for functions of multidimensional arrays is presented. The definition is valid for third‐order tensors in the tensor t‐product formalism, which regards third‐order tensors as block circulant matrices. The tensor function definition is shown to have similar properties as standard matrix function definitions in fundamental scenarios. To demonstrate the definition's potential in applications, the notion of network communicability is generalized to third‐order tensors and computed for a small‐scale example via block Krylov subspace methods for matrix functions. A complexity analysis for these methods in the context of tensors is also provided.

Lund, Kathryn↗