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Results for “density functional calculation”

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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Ab initio calculation of electron–phonon coupling in monoclinic β-Ga{sub 2}O{sub 3} crystal

The interaction between electrons and vibrational modes in monoclinic β-Ga{sub 2}O{sub 3} is theoretically investigated using ab-initio calculations. The large primitive cell of β-Ga{sub 2}O{sub 3} gives rise to 30 phonon modes all of which are taken into account in transport calculation. The electron-phonon interaction is calculated under density functional perturbation theory and then interpolated using Wannier–Fourier interpolation. The long-range interaction elements between electrons and polar optical phonon (POP) modes are calculated separately using the Born effective charge tensor. The direction dependence of the long-range POP coupling in a monoclinic crystal is explored and is included in the transport calculations. Scattering rate calculations are done using the Fermi golden rule followed by solving the Boltzmann transport equation using the Rode's method to estimate low field mobility. A room temperature mobility of 115 cm{sup 2}/V s is observed. Comparison with recent experimentally reported mobility is done for a wide range of temperatures (30 K–650 K). It is also found that the POP interaction dominates the electron mobility under low electric field conditions. The relative contribution of the different POP modes is analyzed and the mode 21 meV POP is found to have the highest impact on low field electron mobility at room temperature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Significantly increased Raman enhancement on defect-rich O-incorporated 1T-MoS 2 nanosheets

Improving charge transfer is the key to the performance of non-noble metal semiconductor-based surface enhanced Raman scattering (SERS) substrates. In this work, the O-incorporated 1T-MoS 2 nanosheets with rich sulfur defects (ID-MoS 2 ) are obtained by simple calcination of 1T-MoS 2 nanosheets in air atmosphere. Using rhodamine 6G (R6G) as typical probe molecules, ID-MoS 2 nanosheets show ultrahigh Raman enhancement effects with an enhancement factor of 1.24 × 10 7 due to sulfur defects and O incorporation in the 1T-MoS 2 lattice. First-principle density functional theory calculations suggest that the existence of sulfur defects and O incorporation significantly increase the Fermi energy level (E f ) and electronic density of states of ID-MoS 2 . Furthermore, O incorporation can enhance the interactions between the substrate and the adsorbed molecules through electrostatic and hydrogen bonding. All these improve the charge transfer resonance and result in the remarkable SERS activity of ID-MoS 2 nanosheets. This is the first study on the increasing SERS performance of semiconductor substrates by simultaneously employing defect and dopant incorporation. This study provides an approach to optimize the performance of semiconductor-based SERS substrates.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Framework for scalable adsorbate–adsorbate interaction models

Here, we present a framework for physically motivated models of adsorbate–adsorbate interaction between small molecules on transition and coinage metals based on modifications to the substrate electronic structure due to adsorption. We use this framework to develop one model for transition and one for coinage metal surfaces. The models for transition metals are based on the d-band center position, and the models for coinage metals are based on partial charges. The models require no empirical parameters, only two first-principles calculations per adsorbate as input, and therefore scale linearly with the number of reaction intermediates. By theory to theory comparison with explicit density functional theory calculations over a wide range of adsorbates and surfaces, we show that the root-mean-squared error for differential adsorption energies is less than 0.2 eV for up to 1 ML coverage.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation

We report that metal-organic frameworks (MOFs) have received a great deal of attention for their potential in atmospheric filtering, and recent work has shown that catecholate linkers can bind metals, creating MOFs with monocatecholate metal centers and abundant open coordination sites. In this study, M-catecholate systems (with M = Mg 2+ , Sc 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ) were used as computational models of metalated catecholate linkers in MOFs. Nitric oxide (NO) is a radical molecule that is considered an environmental pollutant and is toxic if inhaled in large quantities. Binding NO is of interest in creating atmospheric filters, both at the industrial and personal scale. The binding energies of NO to the metal-catecholate systems were calculated using density functional theory (DFT) and complete active space self-consistent field (CASSCF) followed by second order perturbation (CASPT2). Selectivity was studied by calculating the binding energies of additional guests (CO, NH 3 , H 2 O, N 2 , and CO 2 ). The toxic guests have stronger binding than the benign guests for all metals studied, and NO has significantly stronger binding than other guests for most of the metals studied, suggesting that metal-catecholates are worthy of further study for NO filtration. Finally, certain metal-catecholates also showed potential for separation of N 2 and CO 2 via N 2 activation, which could be relevant for carbon capture or ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Order parameters for symmetry-breaking structural transitions: The tetragonal-monoclinic transition in ZrO 2

Group/subgroup structural phase transitions are exploited in a wide variety of technologies, including those that rely on shape-memory behavior and on transformation toughening. Here, we introduce an approach to identify symmetry-adapted strain and shuffle order parameters for any group/subgroup structural transition between a high-symmetry parent phase and its symmetrically equivalent low-symmetry product phases. We show that symmetry-adapted atomic shuffle order parameters can be determined by the diagonalization of an orbital covariance matrix, formed by taking the covariance among the atomic displacement vectors of all symmetrically equivalent product phase variants. We use this approach to analyze the technologically important tetragonal to monoclinic structural phase transformation of ZrO 2 . We explore the energy landscapes, as calculated with density functional theory, along distinct paths that connect m ZrO 2 to t ZrO 2 and to other m ZrO 2 variants. The calculations indicate favorable pairs of variants and reveal intermediate structures likely to exist at coherent twin boundaries and having relatively low deformation energy. We identify crystallographic features of the monoclinic ZrO 2 variant that make it very sensitive to shape changing strains.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

β-O-4 Bond Cleavage Mechanism for Lignin Model Compounds over Pd Catalysts Identified by Combination of First-Principles Calculations and Experiments

Lignin in lignocellulosic biomass is the only renewable source for aromatic compounds, and effective valorization of lignin remains a significant challenge in biomass conversion processes. Here, we have performed density functional theory calculations and experiments to investigate the cleavage mechanism of the C–O ether bond in the lignin model compound 2-phenoxy-1-phenylethanol with a β-O-4 linkage over a Pd(111) catalyst surface model. We propose the favorable reaction pathway to proceed as follows: the dilignol reactant gets dehydrogenated first on the α-carbon and then on the -OH group to generate its corresponding ketone 2-phenoxy-1-phenylethanone; the ketone continues to get dehydrogenated on the β-carbon by first a equilibrated keto–enol tautomerization to its enol form and then -OH dehydrogenation; finally, the C–O ether bond cleavage happens afterward, leading to one-aromatic-ring surface intermediates followed by hydrogenation to yield acetophenone and phenol.

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

Effect of Na substitution on electronic and optical properties of CuInS{sub 2} chalcopyrite semiconductor

Electronic & optical properties of Na substituted CuNaIn{sub 2}S{sub 4} chalcopyrite semiconductors are significantly modified due to Na substitution in the Cu deficient CuInS{sub 2} semiconductor. These properties are obtained form first principle calculation using density functional theory based tight binding Linear muffin tin orbital method. The presence of Na alters the structural distortion and enhances strengths of Cu d and S p hybridization in CuNaIn{sub 2}S{sub 4}. This effect reduces band gap, in agreement with experimental observations and modify other properties significantly. Calculations of optical matrix elements (OME) and joint density of states (JDOS) show that effects of Na substitution on optical properties come through p–d hybridization and structural distortion. OME contribution is prominent near band edge. Both systems show anisotropic optical properties. - Graphical abstract: The figure shows the band structure and total density of states of CuNaIn{sub 2}S{sub 4}. It illustrates energy bands at various symmetry points, band gap and contribution of various orbitals.

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

Molecular-Scale Characterization of Photoinduced Charge Separation in Mixed-Dimensional InSe–Organic van der Waals Heterostructures

Layered indium selenide (InSe) is an emerging two-dimensional semiconductor that has shown significant promise for high-performance transistors and photodetectors. The range of optoelectronic applications for InSe can potentially be broadened by forming mixed-dimensional van der Waals heterostructures with zero-dimensional molecular systems that are widely employed in organic electronics and photovoltaics. Here, we report the spatially resolved investigation of photoinduced charge separation between InSe and two molecules (C 70 and C 8 -BTBT) using scanning tunneling microscopy combined with laser illumination. We experimentally and computationally show that InSe forms type-II and type-I heterojunctions with C 70 and C 8 -BTBT, respectively, due to an interplay of charge transfer and dielectric screening at the interface. Laser-excited scanning tunneling spectroscopy reveals a ~0.25 eV decrease in the energy of the lowest unoccupied molecular orbital of C 70 with optical illumination. Furthermore, photoluminescence spectroscopy and Kelvin probe force microscopy indicate that electron transfer from InSe to C 70 in the type-II heterojunction induces a photovoltage that quantitatively matches the observed downshift in the tunneling spectra. In contrast, no significant changes are observed upon optical illumination in the type-I heterojunction formed between InSe and C 8 -BTBT. Density functional theory calculations further show that, despite the weak coupling between the molecular species and InSe, the band alignment of these mixed-dimensional heterostructures strongly differs from the one suggested by the ionization potential and electronic affinities of the isolated components. Self-energy-corrected density functional theory indicates that these effects are the result of the combination of charge redistribution at the interface and heterogeneous dielectric screening of the electron–electron interactions in the heterostructure. In addition to providing specific insight for mixed-dimensional InSe–organic van der Waals heterostructures, this work establishes a general experimental methodology for studying localized charge transfer at the molecular scale that is applicable to other photoactive nanoscale systems.

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

Predicting a quaternary tungsten oxide for sustainable photovoltaic application by density functional theory

A quaternary oxide, CuSnW{sub 2}O{sub 8} (CTTO), has been predicted by density functional theory (DFT) to be a suitable material for sustainable photovoltaic applications. CTTO possesses band gaps of 1.25 eV (indirect) and 1.37 eV (direct), which were evaluated using the hybrid functional (HSE06) as a post-DFT method. The hole mobility of CTTO was higher than that of silicon. Further, optical absorption calculations demonstrate that CTTO is a better absorber of sunlight than Cu{sub 2}ZnSnS{sub 4} and CuIn{sub x}Ga{sub 1−x}Se{sub 2} (x = 0.5). In addition, CTTO exhibits rigorous thermodynamic stability comparable to WO{sub 3}, as investigated by different thermodynamic approaches such as bonding cohesion, fragmentation tendency, and chemical potential analysis. Chemical potential analysis further revealed that CTTO can be synthesized at flexible experimental growth conditions, although the co-existence of at least one secondary phase is likely. Finally, like other Cu-based compounds, the formation of Cu vacancies is highly probable, even at Cu-rich growth condition, which could introduce p-type activity in CTTO.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra

The synthesis, structure, and characterization of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra are reported. Pb{sub 2}O[BO{sub 2}(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb{sub 2}O[BO{sub 2}(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb{sup 2+} cation should be stereoactive. - Graphical abstract: An indirect gap compound of Pb{sub 2}O[BO{sub 2}(OH)] with 2D inorganic layers motif based on OPb{sub 4} tetrahedra has been synthesized and full characterized by crystallographic, IR, TG, UV–vis-NIR Diffuse Reflectance, and theoretical calculations. Display Omitted - Highlights: • A centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] was synthesized and characterized. • The crystalstructure, electronic band and density states was analyzed. • The lone-pair electrons of Pb{sup 2+} were proved to be stereoactive.

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

DFT study on cysteine adsorption mechanism on Au(111) and Au(110)

Periodic density functional theory calculations were used to investigate relevant aspects of adsorption mechanisms of cysteine dimers in protonated form on Au(111) and Au(110) surfaces. The projected densities of states are explicitly discussed for all main chemical groups of cysteine, i.e. the amino group (NH2), the thiol group (SH) and the carboxylic group (COOH) to identify differences in adsorption mechanism. Special emphasis is put on the analysis of changes in the electronic structure of molecules adsorbed on Au(111) and Au(110) surfaces as well as the accompanying charge transfer mechanisms at molecule-substrate interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Evaluation of Thermal Neutron Scattering Law and Cross Sections for Calcium Hydride

Presented in this paper are the calculated thermal scattering law (TSL) and thermal neutron scattering cross sections for Calcium Hydride, hereafter referred to by its chemical symbol CaH 2 . The only other such data prior to this evaluation are thermal neutron scattering libraries in the JEFF database, which suffer from nonphysical features and inaccuracies. The data in this evaluation are calculated from first principles; Density Functional Theory (DFT) is used to calculate the phonon density of states (DOS), which is the primary input required to calculate the TSL. The TSL and cross sections have been evaluated for the three non-equivalent atom cites in the CaH 2: Ca, H 1 , and H 2 . Each evaluation has been submitted to the NNDC for consideration in the next ENDF/B release.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Atomic-resolution characterization of the effects of CdCl{sub 2} treatment on poly-crystalline CdTe thin films

Poly-crystalline CdTe thin films on glass are used in commercial solar-cell superstrate devices. It is well known that post-deposition annealing of the CdTe thin films in a CdCl{sub 2} environment significantly increases the device performance, but a fundamental understanding of the effects of such annealing has not been achieved. In this Letter, we report a change in the stoichiometry across twin boundaries in CdTe and propose that native point defects alone cannot account for this variation. Upon annealing in CdCl{sub 2}, we find that the stoichiometry is restored. Our experimental measurements using atomic-resolution high-angle annular dark field imaging, electron energy-loss spectroscopy, and energy dispersive X-ray spectroscopy in a scanning transmission electron microscope are supported by first-principles density functional theory calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Composition and Structure of (Zr{sub 0.37}Ti{sub 0.63}){sub 3}AlC{sub 2} MAX Phase Crystals Prepared by Self-Propagating High-Temperature Synthesis

A (Zr{sub 0.37}Ti{sub 0.63}){sub 3}AlC{sub 2} MAX phase has been prepared by self-propagating high-temperature synthesis. The composition of its crystals has been determined by comparing X-ray structure analysis results with structural data for (Zr{sub x}Ti{sub 1–x}){sub 3}AlC{sub 2} (0 < x < 1) crystals prepared by other methods. Comparison of X-ray structure analysis data with density functional theory calculation results indicates that the arrangement of the Zr and Ti atoms in the metal–carbon layer is disordered.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Unraveling Excitonic Effects for the First Hyperpolarizabilities of Chromophore Aggregates

Excitonic interactions often significantly affect the optoelectronic properties of molecular materials. However, their role in determining the nonlinear optical response of organic electro-optic materials remains poorly understood. In this paper, we explore the effects of excitonic interactions on the first hyperpolarizability for aggregates of donor–acceptor chromophores. We show that calculations of the first hyperpolarizabilty of chromophore aggregates based on a two-state model agree well with the more rigorous coupled perturbed Hartree–Fock method. We then use both time-dependent density functional theory calculations and the molecular exciton approximation to parametrize the two-state model. Use of the molecular exciton approximation to the two-state model (i) is appropriate for disordered aggregates (unlike band theory), (ii) is computationally efficient enough for calculating the first hyperpolarizability of materials that consist of thousands of interacting chromophores, and (iii) allows the unraveling of the effects of both excitonic interactions and electrostatic polarization of the chromophore electron density by its environment on the first hyperpolarizability of molecular materials. We find that use of the molecular exciton approximation to the two-state model does not introduce significant additional errors compared to those introduced by applying the two-state model alone. We determine that the absolute change to the first hyperpolarizability of chromophore aggregates due to excitonic interactions increases with the size of the aggregate. For all sizes of disordered aggregates of chromophores considered in this paper, the inclusion of excitonic interactions on average decreases the magnitude of the first hyperpolarizability by 12–14% compared to the case of non-interacting chromophores. Lastly, we present a method for analytically calculating the first hyperpolarizability of a one-dimensional periodic array of chromophores within the molecular exciton approximation to the two-state model. This technique can be used to include an approximate correction for excitonic effects when simulating the electro-optic response of disordered and ordered organic materials.

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

Observation of Surface-Bound Negatively Charged Hydride and Hydroxide on GaP(110) in H 2 O Environments

Surface-bound species on GaP(110) formed upon interaction with water were investigated through experiment and theory. These studies are motivated by and discussed in the context of electrocatalytic and photoelectrocatalytic schemes for solar fuel production, including especially observations of selective CO 2 reduction to methanol in acidified aqueous solutions of CO 2 and nitrogen-containing heteroaromatics. Experimentally, surface-bound species over ten orders of magnitude of pressure were spectroscopically identified in situ using synchrotron-based ambient pressure photoelectron spectroscopy (APPES). Ga 3d and O 1s core-level spectra indicate that the interaction of GaP(110) with H 2 O induces formation of a partially dissociated adlayer, characterized by the presence of both Ga-OH and molecular H 2 O species. Measurements of the P 2p core level indicate formation of a negatively charged hydride that irreversibly bonds to surface P in vacuum. The surface densities of the hydroxide and hydride species increase with increasing pressure (surface coverage) of water. Periodic slab calculations using density functional theory were used to study several relevant water configurations at 298 K on this surface. Consistent with earlier theoretical predictions at 0 K, the calculations confirm that Ga-OH, molecular H 2 O, and P-H species are thermodynamically stable on the GaP(110) surface under experimental conditions. Isobaric measurements at elevated pressures were used to probe the thermal stabilities of adsorbed species as well as the oxidation of surface Ga and P. The observation of stable surface hydride formation induced by interaction with water is especially notable given the critical role of hydride transfer to catalysts and CO 2 during chemical fuel synthesis reactions in aqueous environments. Furthermore, it is hypothesized that the observed high stability of the hydride on GaP may contribute to its associated remarkable near-100% faradaic efficiency for methanol generation by solar-driven CO 2 reduction in acidified aqueous pyridine solutions [J. Am. Chem. Soc. 2008, 130, 6342], because such stability is known to yield high overpotentials for the competing hydrogen evolution reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Controlling extrapolations of nuclear properties with feature selection

Predictions of nuclear properties far from measured data are inherently inaccurate because of uncertainties in our knowledge of nuclear forces and in our treatment of quantum many-body effects in strongly-interacting systems. While the model bias can be directly calculated when experimental data is available, only an estimate can be made in the absence of such measurements. Current approaches to compute the estimated bias quickly lose predictive power when their input variables are taken far from the training region, resulting in uncontrolled uncertainties in applications such as nucleosynthesis simulations. In this letter, we present a novel technique to identify the input variables of machine learning algorithms that can provide robust estimates of model bias. Our process is based on selecting input variables, or features, based on their probability distribution functions across the entire nuclear chart. We illustrate our approach on the problem of quantifying the model bias in nuclear binding energies calculated with Density Functional Theory (DFT). We prove that building model biases with only Z and N as features leads to highly unreliable extrapolations. Conversely, we show that proper feature selection can systematically improve theoretical predictions without increasing uncertainties.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2018

Insights on the Synthesis, Crystal and Electronic Structures, and Optical and Thermoelectric Properties of Sr 1– x Sb x HfSe 3 Orthorhombic Perovskite

We report single-phase polycrystalline powders of Sr 1–x Sb x HfSe 3 (x = 0, 0.005, 0.01), a new member of the chalcogenide perovskites, were synthesized using a combination of high temperature solid-state reaction and mechanical alloying approaches. Structural analysis using single-crystal as well as powder X-ray diffraction revealed that the synthesized materials are isostructural with SrZrSe 3 , crystallizing in the orthorhombic space group Pnma (#62) with lattice parameters a = 8.901(2) Å; b = 3.943(1) Å; c = 14.480(3) Å; and Z = 4 for the x = 0 composition. Thermal conductivity data of SrHfSe 3 revealed low values ranging from 0.9 to 1.3 W m –1 K –1 from 300 to 700 K, which is further lowered to 0.77 W m –1 K –1 by doping with 1 mol % Sb for Sr. Electronic property measurements indicate that the compound is quite insulating with an electrical conductivity of 2.9 S/cm at 873 K, which was improved to 6.7 S/cm by 0.5 mol % Sb doping. Thermopower data revealed that SrHfSe 3 is a p-type semiconductor with thermopower values reaching a maximum of 287 μV/K at 873 K for the 1.0 mol % Sb sample. The optical band gap of Sr 1–x Sb x HfSe 3 samples, as determined by density functional theory calculations and the diffuse reflectance method, is ~1.00 eV and increases with Sb concentration to 1.15 eV. Careful analysis of the partial densities of states (PDOS) indicates that the band gap in SrHfSe 3 is essentially determined by the Se-4p and Hf-5d orbitals with little to no contribution from Sr atoms. Typically, band edges of p- and d-character are a good indication of potentially strong absorption coefficient due to the high density of states of the localized p and d orbitals. This points to potential application of SrHfSe3 as absorbing layer in photovoltaic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗