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At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Maximum energy product at elevated temperatures for hexagonal strontium ferrite (SrFe12O19) magnet

The electronic structure of hexagonal strontium ferrite (SrFe12O19) was calculated based on the density functional theory (DFT) and generalized gradient approximation (GGA). The GGA+U method was used to improve the description of localized Fe 3d electrons. Three different effective U (U-eff) values of 3.7, 7.0, and 10.3 eV were used to calculate three sets of exchange integrals for 21 excited states. We then calculated the temperature dependence of magnetic moments m(T) for the five sublattices (2a, 2b, 12k, 4f(1), and 4f(2)) using the exchange integrals. The m(T) of the five sublattices are inter related to the nearest neighbors, where the spins are mostly anti-ferromagnetically coupled. The five sublattice m(T) were used to ()brain the saturation magnetization M-s(T) of SrFe12O19, which is in good agreement with the experimental values. The temperature dependence of maximum energy product. ((BII)(max)(T)) was calculated using the calculated M-s(T). (C) 2013 Elsevier B.V. All rights reserved.

Park, J↗
DOE OSTI2021

Quantum Embedding Theory for Strongly Correlated States in Materials

Quantum embedding theories are promising approaches to investigate strongly correlated electronic states of active regions of large-scale molecular or condensed systems. Notable examples are spin defects in semiconductors and insulators. We present a detailed derivation of a quantum embedding theory recently introduced, which is based on the definition of effective Hamiltonians. The effect of the environment on a chosen active space is accounted for through screened Coulomb interactions evaluated using density functional theory. Importantly, the random phase approximation is not required, and the evaluation of virtual electronic orbitals is circumvented with algorithms previously developed in the context of calculations based on many-body perturbation theory. In addition, we generalize the quantum embedding theory to active spaces composed of orbitals that are not eigenstates of Kohn–Sham Hamiltonians. Finally, we report results for spin defects in semiconductors.

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

Shadow Molecular Dynamics and Atomic Cluster Expansions for Flexible Charge Models

Here, a shadow molecular dynamics scheme for flexible charge models is presented where the shadow Born–Oppenheimer potential is derived from a coarse-grained approximation of range-separated density functional theory. The interatomic potential, including the atomic electronegativities and the charge-independent short-range part of the potential and force terms, is modeled by the linear atomic cluster expansion (ACE), which provides a computationally efficient alternative to many machine learning methods. The shadow molecular dynamics scheme is based on extended Lagrangian (XL) Born–Oppenheimer molecular dynamics (BOMD). XL-BOMD provides stable dynamics while avoiding the costly computational overhead associated with solving an all-to-all system of equations, which normally is required to determine the relaxed electronic ground state prior to each force evaluation. To demonstrate the proposed shadow molecular dynamics scheme for flexible charge models using atomic cluster expansion, we emulate the dynamics generated from self-consistent charge density functional tight-binding (SCC-DFTB) theory using a second-order charge equilibration (QEq) model. The charge-independent potentials and electronegativities of the QEq model are trained for a supercell of uranium oxide (UO 2 ) and a molecular system of liquid water. The combined ACE+XL-QEq molecular dynamics simulations are stable over a wide range of temperatures both for the oxide and for the molecular systems and provide a precise sampling of the Born–Oppenheimer potential energy surfaces. Accurate ground Coulomb energies are produced by the ACE-based electronegativity model during an NVE simulation of UO 2 , predicted to be within 1 meV of those from SCC-DFTB on average during comparable simulations.

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

DFT Accurate Interatomic Potential for Molten NaCl from Machine Learning

Molten alkali chloride salts are a critical component in concentrated solar power and nuclear applications. Despite their ubiquity, the extreme chemical reactivity of molten alkali chlorides at high temperatures has presented a significant challenge in characterizing atomic structures and dynamic properties experimentally. In this work, we we investigate molten NaCl by performing high temperature molecular dynamics simulations using a Gaussian Approximation Potential (GAP) trained on Density Functional Theory (DFT) datasets. Our GAP model, trained with a meager 1000 atomic configurations, arrives at near ab initio accuracy with a mean absolute error of 1.5 meV/atom thus enabling fast analysis of high temperature salt properties on large length (5000 ion pairs) and time (> 1ns) scales currently inaccessible to ab initio simulations. Calculated structure factors and diffusion constants from our GAP model simulations show excellent agreement with experiments. Our results indicate that GAP models are able to capture the many-body interactions required to accurately model ionic-systems.

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

Computation of the Thermal Expansion Coefficient of Graphene with Gaussian Approximation Potentials

Direct experimental measurement of thermal expansion coefficient without substrate effects is a challenging task for two-dimensional (2D) materials, and its accurate estimation with large-scale ab initio molecular dynamics is computationally very expensive. Machine learning-based interatomic potentials trained with ab initio data have been successfully used in molecular dynamics simulations to decrease the computational cost without compromising the accuracy. In this work, we investigated using Gaussian approximation potentials to reproduce the density functional theory-level accuracy for graphene within both lattice dynamical and molecular dynamical methods, and to extend their applicability to larger length and time scales. Two such potentials are considered, GAP17 and GAP20. GAP17, which was trained with pristine graphene structures, is found to give closer results to density functional theory calculations at different scales. Further vibrational and structural analyses verify that the same conclusions can be deduced with density functional theory level in terms of the reasoning of the thermal expansion behavior, and the negative thermal expansion behavior is associated with long-range out-of-plane phonon vibrations. Thus, it is argued that the enabled larger system sizes by machine learning potentials may even enhance the accuracy compared to small-size-limited ab initio molecular dynamics.

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

Pathways of Growth of CdSe Nanocrystals from Nucleant (CdSe) 34 Clusters

The first steps in the growth of quantum platelets from the wurtzite-type (CdSe) 34 clusters are simulated using density functional theory with the generalized gradient approximation. The nucleant (CdSe) 34 cluster has been chosen for simulations because it has experimentally been discovered to be a magic-size nucleant for the low-temperature growth of CdSe quantum platelets. According to the results of our calculations, the growth is anisotropic and favors the (0001) direction, which is consistent with the experimental findings. We discover that growth in other directions lowers the symmetry of the resulting clusters and that the asymmetrical positioning of rhombic defects causes the growing platelet to bend due to the surface strain, which appears to be the limiting factor of growth. An alternative pathway to quantum platelet growth could proceed via the decomposition of (CdSe) 34 to (CdSe) 13 in electron-donating media, which was found to be thermodynamically favorable. Side product (CdSe) 21 generated in this process is capable of growing via hexagonal stacking as well as propagating as a nanotube.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Exciton-Defect Interaction and Optical Properties from a First-Principles T-Matrix Approach

Understanding exciton-defect interactions is critical for optimizing optoelectronic and quantum information applications in many materials. However, ab initio simulations of material properties with defects are often limited to high defect density. Here, we study effects of exciton-defect interactions on optical absorption and photoluminescence spectra in monolayer MoS 2 using a first-principles T-matrix approach. We demonstrate that exciton-defect bound states can be captured by the disorderaveraged Green’s function with the T-matrix approximation and further analyze their optical properties. Our approach yields photoluminescence spectra in good agreement with experiments and provides a new, computationally efficient framework for simulating optical properties of disordered 2D materials from firstprinciples.

T-matrix↗
DOE OSTI2014

Alumina(0001)/Water Interface: Structural Properties and Infrared Spectra from First-Principles Molecular Dynamics Simulations

We investigated the atomic structure and infrared spectra of the alumina(0001)/water interface, using first-principles molecular dynamics simulations based on density functional theory within the generalized gradient approximation. The computed structural properties of the interface are in good agreement with the results of synchrotron X-ray experiments. In this work detailed analyses of the computed infrared spectra revealed two types of water molecules at the hydrophilic oxide/water interface: molecules participating in strong “ice-like” hydrogen bonding with the oxide surface and molecules involved in weaker “liquid-like” hydrogen bonding. Our results provide a molecular interpretation of the “ice-like” and “liquid-like” bands observed in sum-frequency vibrational spectroscopy experiments and underscore the significance of strong hydrogen-bonding interactions in determining the orientation of interfacial water molecules.

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

Effect of hydrogenation on the structure and magnetic properties of an iron oxide cluster

The structure and properties of the Fe8O12Hn clusters (n = 0–18) are computed using the all-electron density functional theory with the generalized gradient approximation for the exchange–correlation potential. The ground state of Fe8O12 is found to be a singlet state having a bi-capped octahedron geometry. Upon hydrogenation, the octahedral framework of Fe is retained in Fe8O12Hn up to n < 7, beyond which point the iron octahedron transforms into a cube. Hydrogen atoms are bound to oxygen atoms up to n = 12, but they bind to the faces of the Fe8 cube when n > 12. The total spin magnetic moment of a Fe8O12Hn cluster is larger than 6 μB for 1 ≤ n ≤ 18, except for n = 8 and 10, where the lowest total energy states are antiferromagnetic singlets. The reason for this deviation from the general behavior in the Fe8O12Hn series is attributed to the collective superexchange phenomenon. Surprisingly, the total spin magnetic moment of a Fe8O12Hn cluster is found to be substantially larger than the total spin magnetic moment of the bare Fe8 cluster when n = 12–18. All of the Fe8O12Hn clusters are stable with respect to an abstraction of a single hydrogen atom but are unstable toward the abstraction of an H2 dimer when n =10 and n = 14–18.

Gutsev, G. L.↗
DOE OSTI2020

Re-evaluation of the TSL for Yttrium Hydride

Yttrium hydride (YH x ) is of interest as a high-temperature moderator material in advanced nuclear reactor systems because of its superior ability to retain hydrogen at elevated temperatures. Thermal neutron scattering laws (TSL) for hydrogen bound in yttrium hydride (H-YH 2 ) and yttrium bound in yttrium hydride (Y-YH 2 ) were previously evaluated by Naval Nuclear Laboratory using the ab initio approach and released in ENDF/B-VIII.0. In that work, density functional theory, incorporating the generalized gradient approximation (GGA) for the exchange-correlation energy, was used to simulate the face-centered cubic structure of YH 2 and calculate the interatomic Hellmann-Feynman forces for a 2×2×2 supercell containing 96 atoms. Lattice dynamics calculations using PHONON were used to determine the phonon density of states. The calculated phonon density of states for H and Y in YH 2 were then used to prepare H-YH 2 and Y-YH 2 TSL evaluations, in the incoherent approximation, using the LEAPR module of NJOY. In addition, elastic scattering was assumed to be incoherent for both H and Y. While the incoherent elastic scattering approximation is appropriate for H-YH 2 , it introduces an undesirable approximation for Y-YH 2 . In this work, we re-evaluate the TSL for Y-YH 2 using FLASSH (Full Law Analysis Scattering System Hub). Y-YH 2 is evaluated using the FLASSH generalized coherent elastic scattering capability in order to capture the Bragg peaks associated with the YH 2 crystal structure which were neglected in the prior NJOY-based evaluation due to limitations in LEAPR. An experimental approach to validate the Y-YH 2 TSL using neutron transmission measurements is discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2011

Protein immobilization and detection on laser processed polystyrene surfaces

The bovine serum albumin (BSA)-polystyrene (PS) interface layer is laser photo activated at 157 nm for site selective multiple target-protein immobilization. The 5-15 nm photon induced interface layer has different chemical, wetting, and stiffness properties than the PS photon processed surface. The irradiated areas exhibit target-protein binding, followed by localized probe-target protein detection. The photon induced chemical modification of the BSA-PS interface layer is identified by: (1) Morphological, imaging, and analysis of surface parameters with atomic force microscopy, (2) spectroscopic shift (4 cm{sup -1}), of the amide I group and formation of new C=N, NH{sub 2}, C-O, C=O, and O-C=O groups following irradiation, identified with attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and (3) the different hydrophilic/hydrophobic and force-distance response of the bare PS and BSA-PS surfaces. Near field edge diffraction (Fresnel) fluorescence imaging specifies the threshold photon energy and the fluence required to optically detect the protein binding on the photon induced BSA-PS interface layer. By approximating the Fresnel integrals with analytical functions, the threshold photon energy and the fluence are expressed as the sum of zero, first, and second order harmonic terms of two characteristic diffracted modes and they are specified to be 8.73x10{sup -9} Jand623 J m{sup -2}, respectively. Furthermore, a bioarray of three probe-target proteins is fabricated with 1.5 {mu}m spatial resolution using a 157 nm laser microstepper. The methodology eliminates the use of intermediate polymer layers between the blocking BSA protein and the PS substrate in bioarray fabrication.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

Accurate quantum dynamics calculations using symmetrized Gaussians on a doubly dense Von Neumann lattice

In a series of earlier articles [B. Poirier, J. Theor. Comput. Chem. 2, 65 (2003); B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004); and ibid. 121, 1704 (2004)], a new method was introduced for performing exact quantum dynamics calculations. The method uses a 'weylet' basis set (orthogonalized Weyl-Heisenberg wavelets) combined with phase space truncation, to defeat the exponential scaling of CPU effort with system dimensionality-the first method ever able to achieve this long-standing goal. Here, we develop another such method, which uses a much more convenient basis of momentum-symmetrized Gaussians. Despite being non-orthogonal, symmetrized Gaussians are collectively local, allowing for effective phase space truncation. A dimension-independent code for computing energy eigenstates of both coupled and uncoupled systems has been created, exploiting massively parallel algorithms. Results are presented for model isotropic uncoupled harmonic oscillators and coupled anharmonic oscillators up to 27 dimensions. These are compared with the previous weylet calculations (uncoupled harmonic oscillators up to 15 dimensions), and found to be essentially just as efficient. Coupled system results are also compared to corresponding exact results obtained using a harmonic oscillator basis, and also to approximate results obtained using first-order perturbation theory up to the maximum dimensionality for which the latter may be feasibly obtained (four dimensions).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

On the neutrinoless double β{sup +}/EC decays

The neutrinoless double positron-emission/electron-capture (0νβ{sup +}/EC) decays are studied for the magnitudes of the involved nuclear matrix elements (NMEs). Decays to the ground state, 0{sub gs}{sup +}, and excited 0{sup +} states are discussed. The participant many-body wave functions are evaluated in the framework of the quasiparticle random-phase approximation (QRPA). Effective, G-matrix-derived nuclear forces are used in realistic single-particle model spaces. The channels β{sup +}β{sup +}, β{sup +}EC, and the resonant neutrinoless double electron capture (R0νECEC) are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Non-adiabatic processes in the charge transfer reaction of O{sub 2} molecules with potassium surfaces without dissociation

Thin potassium films grown on Si(001) substrates are used to measure internal chemicurrents and the external emission of exoelectrons simultaneously during adsorption of molecular oxygen on K surfaces at 120 K. The experiments clarify the dynamics of electronic excitations at a simple metal with a narrow valence band. X-ray photoemission reveals that for exposures below 5 L almost exclusively peroxide K{sub 2}O{sub 2} is formed, i.e., no dissociation of the molecule occurs during interaction. Still a significant chemicurrent and a delayed exoelectron emission are detected due to a rapid injection of unoccupied molecular levels below the Fermi level. Since the valence band width of potassium is approximately equal to the potassium work function (2.4 eV) the underlying mechanism of exoemission is an Auger relaxation whereas chemicurrents are detected after resonant charge transfer from the metal valence band into the injected level. The change of the chemicurrent and exoemission efficiencies with oxygen coverage can be deduced from the kinetics of the reaction and the recorded internal and external emission currents traces. It is shown that the non-adiabaticity of the reaction increases with coverage due to a reduction of the electronic density of states at the surface while the work function does not vary significantly. Therefore, the peroxide formation is one of the first reaction systems which exhibits varying non-adiabaticity and efficiencies during the reaction. Non-adiabatic calculations based on model Hamiltonians and density functional theory support the picture of chemicurrent generation and explain the rapid injection of hot hole states by an intramolecular motion, i.e., the expansion of the oxygen molecule on the timescale of a quarter of a vibrational period.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Vibrational frequency scaling factors for correlation consistent basis sets and the methods CC2 and MP2 and their spin-scaled SCS and SOS variants

We present scaling factors for vibrational frequencies calculated within the harmonic approximation and the correlated wave-function methods coupled cluster singles and doubles model (CC2) and Møller-Plesset perturbation theory (MP2) with and without a spin-component scaling (SCS or spin-opposite scaling (SOS)). Frequency scaling factors and the remaining deviations from the reference data are evaluated for several non-augmented basis sets of the cc-pVXZ family of generally contracted correlation-consistent basis sets as well as for the segmented contracted TZVPP basis. We find that the SCS and SOS variants of CC2 and MP2 lead to a slightly better accuracy for the scaled vibrational frequencies. The determined frequency scaling factors can also be used for vibrational frequencies calculated for excited states through response theory with CC2 and the algebraic diagrammatic construction through second order and their spin-component scaled variants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Interaction of ultrashort laser pulses and silicon solar cells under short circuit conditions

Ultrashort pulse lasers are promising tools for numerous measurement purposes. Among other benefits their high peak powers allow for efficient generation of wavelengths in broad spectral ranges and at spectral powers that are orders of magnitude higher than in conventional light sources. Very recently this has been exploited for the establishment of sophisticated measurement facilities for electrical characterization of photovoltaic (PV) devices. As the high peak powers of ultrashort pulses promote nonlinear optical effects they might also give rise to nonlinear interactions with the devices under test that possibly manipulate the measurement outcome. In this paper, we present a comprehensive theoretical and experimental study of the nonlinearities affecting short circuit current (I{sub SC}) measurements of silicon (Si) solar cells. We derive a set of coupled differential equations describing the radiation-device interaction and discuss the nonlinearities incorporated in those. By a semi-analytical approach introducing a quasi-steady-state approximation and integrating a Green's function we solve the system of equations and obtain simulated I{sub SC} values. We validate the theoretical model by I{sub SC} ratios obtained from a double ring resonator setup capable for reproducible generation of various ultrashort pulse trains. Finally, we apply the model to conduct the most prominent comparison of I{sub SC} generated by ultrashort pulses versus continuous illumination. We conclude by the important finding that the nonlinearities induced by ultrashort pulses are negligible for the most common I{sub SC} measurements. However, we also find that more specialized measurements (e.g., of concentrating PV or Si-multijunction devices as well as highly localized electrical characterizations) will be biased by two-photon-absorption distorting the I{sub SC} measurement.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Density-matrix based determination of low-energy model Hamiltonians from ab initio wavefunctions

We propose a way of obtaining effective low energy Hubbard-like model Hamiltonians from ab initio quantum Monte Carlo calculations for molecular and extended systems. The Hamiltonian parameters are fit to best match the ab initio two-body density matrices and energies of the ground and excited states, and thus we refer to the method as ab initio density matrix based downfolding. For benzene (a finite system), we find good agreement with experimentally available energy gaps without using any experimental inputs. For graphene, a two dimensional solid (extended system) with periodic boundary conditions, we find the effective on-site Hubbard U{sup ∗}/t to be 1.3 ± 0.2, comparable to a recent estimate based on the constrained random phase approximation. For molecules, such parameterizations enable calculation of excited states that are usually not accessible within ground state approaches. For solids, the effective Hamiltonian enables large-scale calculations using techniques designed for lattice models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Long-range correction for tight-binding TD-DFT

We present two improvements to the tight-binding approximation of time-dependent density functional theory (TD-DFTB): First, we add an exact Hartree-Fock exchange term, which is switched on at large distances, to the ground state Hamiltonian and similarly to the coupling matrix that enters the linear response equations for the calculation of excited electronic states. We show that the excitation energies of charge transfer states are improved relative to the standard approach without the long-range correction by testing the method on a set of molecules from the database in Peach et al. [J. Chem. Phys. 128, 044118 (2008)] which are known to exhibit problematic charge transfer states. The degree of spatial overlap between occupied and virtual orbitals indicates where TD-DFTB and long-range corrected TD-DFTB (lc-TD-DFTB) can be expected to produce large errors. Second, we improve the calculation of oscillator strengths. The transition dipoles are obtained from Slater Koster files for the dipole matrix elements between valence orbitals. In particular, excitations localized on a single atom, which appear dark when using Mulliken transition charges, acquire a more realistic oscillator strength in this way. These extensions pave the way for using lc-TD-DFTB to describe the electronic structure of large chromophoric polymers, where uncorrected TD-DFTB fails to describe the high degree of conjugation and produces spurious low-lying charge transfer states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗