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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Adsorption and Recovery of Polyphenolic Flavonoids Using TiO 2 -Functionalized Mesoporous Silica Nanoparticles

Exploiting specific interactions with titania (TiO 2 ) has been proposed for the separation and recovery of a broad range of biomolecules and natural products, including therapeutic polyphenolic flavonoids which are susceptible to degradation, such as quercetin. Functionalizing mesoporous silica with TiO 2 has many potential advantages over bulk and mesoporous TiO 2 as an adsorbent for natural products, including robust synthetic approaches leading to high surface area, stable separation platforms. Here, TiO 2 surface functionalized mesoporous silica nanoparticles (MSNPs) are synthesized and characterized as a function of TiO 2 content (up to 636 mg TiO2/g). The adsorption isotherms of two polyphenolic flavonoids, quercetin and rutin, were determined (0.05-10 mg/ml in ethanol), and a 100-fold increase in the adsorption capacity was observed relative to functionalized nonporous particles with similar TiO 2 surface coverage. An optimum extent of functionalization (approximately 440 mg TiO 2 /g particles) is interpreted from characterization techniques including grazing incidence x-ray scattering (GIXS), high resolution transmission electron microscopy (HRTEM) and nitrogen adsorption, which examined the interplay between the extent of TiO 2 functionalization and the accessibility of the porous structures. The recovery of flavonoids is demonstrated using ligand displacement in ethanolic citric acid solution (20% w/v), in which greater than 90% recovery can be achieved in a multistep extraction process. The radical scavenging activity (RSA) of the recovered and particle-bound quercetin as measured by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay demonstrates greater than 80% retention of antioxidant activity by both particle-bound and recovered quercetin. In conclusion, these mesoporous titanosilicate materials can serve as a synthetic platform to isolate, recover, and potentially deliver degradation-sensitive natural products to biological systems.

36 MATERIALS SCIENCE↗
DOE OSTI2017

The Importance of Being Inconsistent

We review the role of self-consistency in density functional theory (DFT). We apply a recent analysis to both Kohn–Sham and orbital-free DFT, as well as to partition DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes between errors in approximate functionals versus errors in the self-consistent density. This yields insights into the origins of many errors in DFT calculations, especially those often attributed to self-interaction or delocalization error. In many classes of problems, errors can be substantially reduced by using better densities. Finally, we review the history of these approaches, discuss many of their applications, and give simple pedagogical examples.

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

Improvements in the orbitalwise scaling down of Perdew–Zunger self-interaction correction in many-electron regions

The Perdew-Zunger (PZ) method offers a way to remove the self-interaction (SI) error from density functional approximations on an orbital by orbital basis. The PZ method provides significant improvements for the properties such as barrier heights or dissociation energies but results in over-correcting the properties well described by SI-uncorrected semi-local functional. One cure to rectify the over-correcting tendency is to scale down the magnitude of SI-correction of each orbital in the many electron region. We have implemented the orbitalwise scaled down SI-correction (OSIC) scheme of Vydrov et al. [J. Chem. Phys. 124, 094108 (2006)] using the Fermi-L owdin SI-correction method. After validating the OSIC implementation with previously reported OSICLSDA results, we examine its performance with the most successful non-empirical SCAN meta-GGA functional. Using different forms of scaling factors to identify one-electron regions, we assess the performance of OSIC-SCAN for a wide range of properties: total energies, ionization potentials and electron affinities for atoms, atomization energies, dissociation and reaction energies, and reaction barrier heights of molecules. Our results show that OSIC-SCAN provides superior results than the previously reported OSIC-LSDA, -PBE, and -TPSS results. Furthermore, we propose selective scaling of OSIC (SOSIC) to remove its major shortcoming that destroys the -1/r asymptotic behavior of the potentials. The SOSIC method gives the highest occupied orbital eigenvalues practically identical to those in PZSIC and unlike OSIC provides bound atomic anions even with larger powers of scaling factors. Furthermore, SOSIC compared to PZSIC or OSIC provides more balanced description of total energies and barrier heights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Microscopic Modeling of Intersubband Resonances in InAs/AlSb Quantum Wells

Linear absorption spectra from intersubband resonance in InAs/AlSb quantum wells are analyzed theoretically using the intersubband semiconductor Bloch equation approach. Our model goes beyond the Hartree-Fock approximation and treats particle-particle correlations under the second Born approximation. Electron-electron and -LO phonon scatterings from such a treatment describe intrinsic line broadening to the intersubband resonance. Electron subbands are determined self-consistently with a spurious-state-free 8-band k.p Hamiltonian under the envelope function approximation. To compare with experimental measurements, we also included line broadening due to electron-interface roughness scattering. Excellent agreement was achieved for temperature-dependent absorption spectra in the mid-infrared frequency range, after taking into careful account the interplay of material parameters, nonparabolicity in bandstructure, and many-body effects.

Li, Jian-Zhong↗
DOE OSTI2020

Experimental Validation of Approximate Dynamic Programming Based Optimization and Convergence on Microgrid Applications

Stochastic optimization can better address uncertainties in power system problems. However, when state space and action space become large, many existing approaches become computationally expensive and even infeasible. Approximate dynamic programming (ADP) attracts researchers’ attention as a powerful tool for solving power system optimization problems with reduced computational cost. In this paper, in light of the existing literature, we investigate how the ADP approach with post-decision value function approximation converges to the nearly optimal solution with improved computational speed and experimentally validate the performance of the approach for a microgrid energy optimization problem. The approximation error versus the number of iteration is studied for convergence analysis of the post-decision ADP. A flowchart is provided to illustrate the proposed ADP algorithm for a microgrid energy optimization problem. The performance of ADP and dynamic programming (DP) is compared in terms of optimization error and computational time. It has found that the post-decision ADP approach can achieve competitive optimality with improved computational speed compared to the traditional DP.

Das, Avijit↗
NASA NTRS1973

New thermodynamic functions for the C3 molecule.

When graphite is used as ablation material in heat shields, very often a prominent carbon species vaporized into the stream is C3. The thermodynamic properties of the C3 molecule are, therefore, important in calculating transport phenomena in the ablation flow field. The nature of the C3 thermodynamic functions has been in doubt because of the uncertain contribution of the bending mode vibrations to the total internal energy of the molecule. An approach for overcoming these difficulties is considered. The results of the computations are presented in the form of graphs and approximating functions.

Pearson, W. E.↗
DOE OSTI2017

Assessing DFT-D3 Damping Functions Across Widely Used Density Functionals: Can We Do Better?

With the aim of improving the utility of the DFT-D3 empirical dispersion correction, we herein generalize the DFT-D3 damping function by optimizing an additional parameter, an exponent, which controls the rate at which the dispersion tail is activated. This method- DFT-D3(op), shorthand for “optimized power,” where power refers to the newly introduced exponent- is then parametrized for use with ten popular density functional approximations across a small set of noncovalent interactions and isomerization energies; the resulting methods are then evaluated across a large independent test set of 2475 noncovalent binding energies and isomerization energies. We find that the DFT-D3(op) tail represents a substantial improvement over existing damping functions, as it affords significant reductions in errors associated with noncovalent interaction energies and geometries. Finally, the revPBE0-D3(op) and MS2-D3(op) methods in particular stand out, and our extensive testing indicates they are competitive with other modern density functionals.

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

Self-interaction correction in water–ion clusters

We study the importance of self-interaction errors in density functional approximations for various water–ion clusters. We have employed the Fermi-Löwdin orbital self-interaction correction (FLOSIC) method in conjunction with LSDA, PBE, and SCAN to describe binding energies of hydrogen-bonded water–ion clusters, i.e., water–hydronium, water– hydroxide, water–halide, as well as non-hydrogen-bonded water–alkali clusters. In the hydrogen-bonded water–ion clusters, the building blocks are linked by hydrogen atoms, although the links are much stronger and longer-ranged than the normal hydrogen bonds between water molecules, because the monopole on the ion interacts with both permanent and induced dipoles on the water molecules. We find that self-interaction errors overbind the hydrogen-bonded water– ion clusters and that FLOSIC reduces the error and brings the binding energies into closer agreement with higher–level calculations. Here, the non-hydrogen-bonded water–alkali clusters are not significantly affected by self-interaction errors. Self-interaction corrected PBE predicts the lowest mean unsigned error in binding energies (≤ 50 meV/H 2 O) for hydrogen-bonded water–ion clusters. Self-interaction errors are also largely dependent on the cluster size, and FLOSIC does not accurately capture the subtle variation in all clusters, indicating the need for further refinement.

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

G 0 W 0 Ionization Potentials of First-Row Transition Metal Aqua Ions

Here, we report computations of the vertical ionization potentials within the GW approximation of the near-complete series of first-row transition metal (V–Cu) aqua ions in their most common oxidation states, i.e., V 3+ , Cr 3+ , Cr 2+ , Mn 2+ , Fe 3+ , Fe 2+ , Co 2+ , Ni 2+ , and Cu 2+ . The d-orbital occupancy of these systems spans a broad range from d 2 to d 9 . All of the structures were first optimized at the density functional theory level using a large cluster of explicit water molecules that are embedded in a continuum solvation model. Vertical ionization potentials were computed with the one-shot G 0 W 0 approach on a range of transition metal ion clusters (6, 18, 40, and 60 explicit water molecules), wherein the convergence with respect to the basis set size was evaluated using the systems with 40 water molecules. We assess the results using three different density functional approximations as starting points for the vertical ionization potential calculations, namely, G 0 W 0 @PBE, G 0 W 0 @PBE0, and G 0 W 0 @r 2 SCAN. While the predicted ground-state structures are similar to all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with experiment when using the G 0 W 0 @PBE0 and G 0 W 0 @r 2 SCAN approaches, with the r 2 SCAN-based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures are in good agreement with available experimental data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Accuracy of Density Functional Theory Methods for the Calculation of Magnetic Exchange Couplings in Binuclear Iron(III) Complexes

We assess the performance of popular hybrid density functional approximations for the prediction of magnetic exchange couplings (J) in FeIII complexes. To this end, eleven dinuclear oxo-bridged iron(III) complexes with accurately determined J values were chosen to cover cases of weak and strong antiferromagnetic couplings ranging from -6 cm -1 to -132 cm -1 . Six representative exchange-correlation functionals ranging from the hybrids PBE and B3LYP to meta hybrids (M06, M062X), range separated functionals (HSE, LC-!PBE), and LSDA with 30 % of HF exchange were used for this assessment. These functionals have been suggested as good performers for this particular property in transition metal complexes and hence this assessment aims to narrow the interval of con dence for the particular case of Fe complexes. In addition, we examined the performance of an alternative method based on di erential local spin rotations to calculate magnetic exchange coupling parameters in these complexes. Our results show that, although some of these functionals perform on par, the M06 and HSE functionals yields magnetic exchange couplings in closer agreement with experimental data, with a mean absolute percentage errors of 8.6 and 9.2 %, respectively.

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

Spin–Orbit Matrix Elements for a Combined Spin-Flip and IP/EA approach

We introduce a practical approach for computing the Breit–Pauli spin–orbit matrix elements of multiconfigurational systems with both spin and spatial degeneracies based on our recently developed RAS-nSF-IP/EA method (Houck, S. E.; et al. J. Chem. Theory Comput. 2019, 15, 2278). The spin–orbit matrix elements over all the multiplet components are computed using a single one-particle reduced density matrix as a result of the Wigner–Eckart theorem. A mean field spin–orbit approximation was used to account for the two-electron contributions. Basis set dependence as well as the effect of including additional excitations is presented. The effect of correlating the core and semicore orbitals is also examined. Surprisingly accurate results are obtained for spin–orbit coupling constants, despite the fact that the efficient wave function approximations we research neglect the bulk of dynamical correlation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Microscopic Modeling of Intersubband Optical Processes in Type II Semiconductor Quantum Wells: Linear Absorption

Linear absorption spectra arising from intersubband transitions in semiconductor quantum well heterostructures are analyzed using quantum kinetic theory by treating correlations to the first order within Hartree-Fock approximation. The resulting intersubband semiconductor Bloch equations take into account extrinsic dephasing contributions, carrier-longitudinal optical phonon interaction and carrier-interface roughness interaction which is considered with Ando s theory. As input for resonance lineshape calculation, a spurious-states-free 8-band kp Hamiltonian is used, in conjunction with the envelop function approximation, to compute self-consistently the energy subband structure of electrons in type II InAs/AlSb single quantum well structures. We demonstrate the interplay of nonparabolicity and many-body effects in the mid-infrared frequency range for such heterostructures.

Li, Jian-Zhong↗
DOE OSTI2023

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within “chemical accuracy” (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N7) computational cost. In addition, a hierarchy of density functional approximations of increasing formal sophistication, known as Jacob’s ladder, has been shown to systematically reduce average errors over large datasets representing weakly correlated chemistry. However, the accuracy of such computational models is less clear in the increasingly important frontiers of chemical space including transition metals and f-block compounds, in which strong correlation can play an important role in reactivity. A stochastic method, phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), has been shown to be capable of producing chemically accurate predictions even for challenging molecular systems beyond the main group, with relatively low O(N3 − N4) cost and near-perfect parallel efficiency. Herein, we present our perspectives on the past, present, and future of the ph-AFQMC method. We focus on its potential in transition metal quantum chemistry to be a highly accurate, systematically improvable method that can reliably probe strongly correlated systems in biology and chemical catalysis and provide reference thermochemical values (for future development of density functionals or interatomic potentials) when experiments are either noisy or absent. Finally, we discuss the present limitations of the method and where we expect near-term development to be most fruitful.

Chemistry↗
DOE OSTI2018

Thermal expansion in dispersion-bound molecular crystals

In this paper, we explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with ab initio molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridinelike molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I (≈ 40% more than classical thermal expansion at 153 K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. Finally, when predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and more sophisticated density functional approximations improve the accuracy of the theoretical model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Quantum Chemical Calculation of p K a s of Environmentally Relevant Functional Groups: Carboxylic Acids, Amines, and Thiols in Aqueous Solution

Developing accurate quantum chemical approaches for calculating p K a s is of broad interest. Useful accuracy can be obtained by using density functional theory (DFT) in combination with a polarizable continuum solvent model. However, some classes of molecules present problems for this approach, yielding errors greater than 5 p K units. Various methods have been developed to improve the accuracy of the combined strategy. These methods perform well but either do not generalize or introduce additional degrees of freedom, increasing the computational cost. The Solvation Model based on Density (SMD) has emerged as one of the most commonly used continuum solvent models. Nevertheless, for some classes of organic compounds, e.g., thiols, the p K a s calculated with the original SMD model show errors of 6–10 p K units, and we traced these errors to inaccuracies in the solvation free energies of the anions. To improve the accuracy of p K a s calculated with DFT and the SMD model, we developed a scaled solvent-accessible surface approach for constructing the solute–solvent boundary. By using a “direct” approach, in which all quantities are computed in the presence of the continuum solvent, the use of thermodynamic cycles is avoided. Furthermore, no explicit water molecules are required. Three benchmark data sets of experimentally measured p K a values, including 28 carboxylic acids, 10 aliphatic amines, and 45 thiols, were used to assess the optimized SMD model, which we call SMD with a scaled solvent-accessible surface (SMD sSAS ). Of the methods tested, the M06-2X density functional approximation, 6-31+G(d,p) basis set, and SMD sSAS solvent model provided the most accurate p K a s for each set, yielding mean unsigned errors of 0.9, 0.4, and 0.5 p K units, respectively, for carboxylic acids, aliphatic amines, and thiols. As a result, this approach is therefore useful for efficiently calculating the p K a s of environmentally relevant functional groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

An analytical technique for approximating unsteady aerodynamics in the time domain

An analytical technique is presented for approximating unsteady aerodynamic forces in the time domain. The order of elements of a matrix Pade approximation was postulated, and the resulting polynomial coefficients were determined through a combination of least squares estimates for the numerator coefficients and a constrained gradient search for the denominator coefficients which insures stable approximating functions. The number of differential equations required to represent the aerodynamic forces to a given accuracy tends to be smaller than that employed in certain existing techniques where the denominator coefficients are chosen a priori. Results are shown for an aeroelastic, cantilevered, semispan wing which indicate a good fit to the aerodynamic forces for oscillatory motion can be achieved with a matrix Pade approximation having fourth order numerator and second order denominator polynomials.

Dunn, H. J.↗
DOE OSTI2021

Scalar field in Reissner–Nordström spacetime: Bound state and scattering state (with appendix on eliminating oscillation in partial sum approximation of periodic function)

Highlights: • Bound-state and scattering-state solutions of massive scalar fields in R-N spacetime. • Bound-state wave functions and eigenvalues of massive scalar fields in R-N spacetime. • Solving explicit expressions of scattering phase shifts by integral equation methods. • Introducing tortoise coordinates for R-N spacetime. • Eliminating oscillations in the partial sum approximation of periodic functions. In this paper, we solve the massive scalar field in the Reissner–Nordström spacetime. The scalar field in the Reissner–Nordström spacetime has both bound states and scattering states. For bound states, we solve the bound-state wave function and the eigenvalue spectrum. For scattering states, we solve the scattering wave function and give an explicit expression for scattering phase shift by the integral equation method. Especially, we introduce the tortoise coordinate for the Reissner–Nordström spacetime. Moreover, in the calculation of scattering cross sections, we encounter a difficulty in partial sum approximation. If the sum of partial waves cannot be performed exactly, one has to turn to the partial sum approximation which approximates a function by the first several terms of the series. However, in the partial sum approximation there exists an incorrect oscillation which cannot be eliminated by keeping more terms. In the appendix we suggest an approach for eliminating such oscillations in the partial sum.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Model selection and parameter estimation in tumor growth models using approximate Bayesian computation-ABC

Cancer is one of the most fatal diseases in the world. Governments and researchers from various areas have continuously concentrated efforts to better understand the disease and propose diagnostic and treatment techniques. The use of mathematical models of tumor growth is of great importance for the development of such techniques. Due to the variety of models nowadays available in the literature, the problems of model selection and parameter estimation come into picture, aiming at suitably predicting the patient’s status of the disease. As the available data on dependent variables of existing models might not justify the use of common likelihood functions, approximate Bayesian computation (ABC) becomes a very attractive tool for model selection and model calibration (parameter estimation) in tumor growth models. In the present study, a Monte Carlo approximate Bayesian computation (ABC) algorithm is applied to select among competing models of tumor growth, with and without chemotherapy treatment. Simulated measurements are used in this work. The results obtained show that the algorithm correctly selects the model and estimates the parameters used to generate the simulated measurements.

60 APPLIED LIFE SCIENCES↗