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Results for “Hybrid DFT”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO 3

We report that rechargeable batteries that utilize divalent Mg ions as the charge carrier species can in principle achieve substantially greater volumetric energy densities than conventional Li-ion batteries. One significant impediment to the development of commercially viable Mg-ion batteries is the slow rate of Mg ion diffusion through otherwise promising cathode materials. Accurate prediction of the activation energies associated with this diffusion process using density functional theory (DFT) is especially challenging due to self-interaction errors intrinsic to DFT that lead to over-delocalization of the d-electrons. One effective but highly computationally demanding approach to reducing self-interaction errors is the use of hybrid functionals, which incorporate a fraction of exact Hartree–Fock exchange. In this work, we assess the effects of exact exchange on computed activation energies for ion diffusion in one potential cathode material, α-MoO 3 . In contrast to previous studies that primarily utilize non-hybrid functionals, we perform nudged elastic band calculations in which the nuclear coordinates are fully converged using both hybrid functionals and k-point sampling. Additionally, it is found that while non-hybrid functionals indicate the existence of thermodynamically accessible channels for bulk Mg ion diffusion in all three dimensions, hybrid functionals predict that some of these channels are largely inaccessible under typical charge/discharge conditions. Furthermore, it is demonstrated that certain commonly used approximations for incorporating the effects of Hartree–Fock exchange are inadequate for this system, including DFT+U calculations and the use of single-point hybrid calculations using atomic positions obtained using non-hybrid functionals.

25 ENERGY STORAGE↗
DOE OSTI2013

A Screened Hybrid DFT Study of Actinide Oxides, Nitrides, and Carbides

A systematic study of the structural, electronic, and magnetic properties of actinide oxides, nitrides, and carbides (AnX1–2 with X = C, N, O) is performed using the Heyd–Scuseria–Ernzerhof (HSE) hybrid functional. Our computed results show that the screened hybrid HSE functional gives a good description of the electronic and structural properties of actinide dioxides (strongly correlated insulators) when compared with available experimental data. However, there are still some problems reproducing the electronic properties of actinide nitrides and carbides (strongly correlated metals). In addition, in order to compare with the results by HSE, the structures, electronic, and magnetic properties of these actinide compounds are also investigated in the PBE and PBE+U approximation. Interestingly, the density of states of UN obtained with PBE compares well with the experimental photoemission spectra, in contrast to the hybrid approximation. This is presumably related to the need of additional screening in the Hartree–Fock exchange term of the metallic phases.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Study of morphology effects on magnetic interactions and band gap variations for 3d late transition metal bi-doped ZnO nanostructures by hybrid DFT calculations

Using density functional theory (DFT) based electronic structure calculations, the effects of morphology of semiconducting nanostructures on the magnetic interaction between two magnetic dopant atoms as well as a possibility of tuning band gaps have been studied in the case of the bi-doped (ZnO){sub 24} nanostructures with the impurity dopant atoms of the 3d late transition metals—Mn, Fe, Co, Ni, and Cu. To explore the morphology effect, three different structures of the host (ZnO){sub 24} nano-system, having different degrees of spatial confinement, have been considered: a two dimensional nanosheet, a one dimensional nanotube, and a finite cage-shaped nanocluster. The present study employs hybrid density functional theory to accurately describe the electronic structure of all the systems. It is shown here that the magnetic coupling between the two dopant atoms remains mostly anti-ferromagnetic in the course of changing the morphology from the sheet geometry to the cage-shaped geometry of the host systems, except for the case of energetically most stable bi-Mn doping, which shows a transition from ferromagnetic to anti-ferromagnetic coupling with decreasing aspect ratio of the host system. The effect of the shape change, however, has a significant effect on the overall band gap variations of both the pristine as well as all the bi-doped systems, irrespective of the nature of the dopant atoms and provides a means for easy tunability of their optoelectronic properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Cholesky-decomposed density MP2 with density fitting: Accurate MP2 and double-hybrid DFT energies for large systems

Our recently developed QQR-type integral screening is introduced in our Cholesky-decomposed pseudo-densities Møller-Plesset perturbation theory of second order (CDD-MP2) method. We use the resolution-of-the-identity (RI) approximation in combination with efficient integral transformations employing sparse matrix multiplications. The RI-CDD-MP2 method shows an asymptotic cubic scaling behavior with system size and a small prefactor that results in an early crossover to conventional methods for both small and large basis sets. We also explore the use of local fitting approximations which allow to further reduce the scaling behavior for very large systems. The reliability of our method is demonstrated on test sets for interaction and reaction energies of medium sized systems and on a diverse selection from our own benchmark set for total energies of larger systems. Timings on DNA systems show that fast calculations for systems with more than 500 atoms are feasible using a single processor core. Parallelization extends the range of accessible system sizes on one computing node with multiple cores to more than 1000 atoms in a double-zeta basis and more than 500 atoms in a triple-zeta basis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Quasiparticle Level Alignment for Photocatalytic Interfaces

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO2(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and G0W0, scQPGW1, scQPGW0, and scQPGW QP calculations. Our results demonstrate that G0W0, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2019

Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling

In this paper, we describe a new computer implementation of electron transfer (ET) theory in extended systems treated by periodic density functional theory (DFT), including the calculation of the electronic coupling transition element V AB . In particular, the development opens up the full characterization of electron transfer in the solid state. The approach is valid for any single-determinant wavefunction with localized character representing the electronic structure of the system, from Hartree–Fock (HF) theory, to density functional theory (DFT), hybrid DFT theory, DFT+U theory, and constrained DFT (cDFT) theory. The implementation in CP2K reuses the high-performance functions of the code. The computational cost is equivalent to only one iteration of an HF calculation. We present test calculations for electron transfer in a number of systems, including a 1D-model of ferric oxide, hematite Fe2O 3 , rutile TiO 2 , and finally bismuth vanadate BiVO 4 .

14 SOLAR ENERGY↗
DOE OSTI2015

Communication: Hole localization in Al-doped quartz SiO{sub 2} within ab initio hybrid-functional DFT

We investigate the long-standing problem of hole localization at the Al impurity in quartz SiO{sub 2}, using a relatively recent DFT hybrid-functional method in which the exchange fraction is obtained ab initio, based on an analogy with the static many-body COHSEX approximation to the electron self-energy. As the amount of the admixed exact exchange in hybrid functionals has been shown to be determinant for properly capturing the hole localization, this problem constitutes a prototypical benchmark for the accuracy of the method, allowing one to assess to what extent self-interaction effects are avoided. We obtain good results in terms of description of the charge localization and structural distortion around the Al center, improving with respect to the more popular B3LYP hybrid-functional approach. We also discuss the accuracy of computed hyperfine parameters, by comparison with previous calculations based on other self-interaction-free methods, as well as experimental values. We discuss and rationalize the limitations of our approach in computing defect-related excitation energies in low-dielectric-constant insulators.

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

Improved treatment of exact exchange in Quantum ESPRESSO

Here, we present an algorithm and implementation for the parallel computation of exact exchange in Quantum ESPRESSO (QE) that exhibits greatly improved strong scaling. QE is an open-source software package for electronic structure calculations using plane wave density functional theory, and supports the use of local, semi-local, and hybrid DFT functionals. Wider application of hybrid functionals is desirable for the improved simulation of electronic band energy alignments and thermodynamic properties, but the computational complexity of evaluating the exact exchange potential limits the practical application of hybrid functionals to large systems and requires efficient implementations. We demonstrate that existing implementations of hybrid DFT that utilize a single data structure for both the local and exact exchange regions of the code are significantly limited in the degree of parallelization achievable. We present a band-pair parallelization approach, in which the calculation of exact exchange is parallelized and evaluated independently from the parallelization of the remainder of the calculation, with the wavefunction data being efficiently transformed on-the-fly into a form that is optimal for each part of the calculation. For a 64 water molecule supercell, our new algorithm reduces the overall time to solution by nearly an order of magnitude.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Play the heavy: An effective mass study for α-Fe{sub 2}O{sub 3} and corundum oxides

Iron(III) oxide (α-Fe{sub 2}O{sub 3}) is a known water splitting catalyst commonly used in photoelectrochemical cells. These cells are severely impaired by poor conductivity in α-Fe{sub 2}O{sub 3}, and resolving the conductivity issue is therefore crucial. One of the most intrinsic properties of matter, which governs conductivity, is the carrier effective masses. In this work, we investigate the carrier effective masses in α-Fe{sub 2}O{sub 3} and other corundum oxides, including Al{sub 2}O{sub 3}, Cr{sub 2}O{sub 3}, Ga{sub 2}O{sub 3}, and In{sub 2}O{sub 3} with different theoretical constructs: density functional theory (DFT), DFT+U, hybrid DFT, and G{sub 0}W{sub 0}. We find DFT sufficiently describes the carrier masses and a quasi-particle theory is only required for accuracies better than 30% for the conduction band effective mass. Additionally, we compare the density of states (DOS) and band effective mass approximations and conclude the DOS effective mass provides poor results whenever the band structure is anisotropic. We find that the charge carriers in Fe{sub 2}O{sub 3} “play the heavy” since they have large effective masses that reduce conductivity and device efficiency. Finally, we conclude that the less heavy electron effective masses of other corundum oxides studied relative to Fe{sub 2}O{sub 3} could contribute to efficiency improvements in Fe{sub 2}O{sub 3} upon Al{sub 2}O{sub 3}, Ga{sub 2}O{sub 3}, and In{sub 2}O{sub 3} coverage.

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

Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

Approximate, semilocal density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical model of catalytic surfaces that both overbind adsorbates yet are also too stable. We investigate the effect of two widely applied approaches for delocalization error correction, (i) affordable DFT+U (i.e., semilocal DFT augmented with a Hubbard U) and (ii) hybrid functionals with an admixture of Hartree–Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water-splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti and V) and decreases adsorbate energies only in later transition metals (e.g., Ir and Pt). Both global and local hybrids destabilize surfaces and reduce adsorbate binding across the periodic table, in agreement with higher-level reference calculations. Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not. We recommend local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semilocal DFT.

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

Transition Metal Oxide Alloys as Potential Solar Energy Conversion Materials

First-row transition metal oxides (TMOs) are inexpensive potentia alternative materials for solar energy conversion devices. However, some TMOs, such as manganese(II) oxide, have band gaps that are too large for efficiently absorbing solar energy. Other TMOs, such as iron(II) oxide, have conduction and valence band edges with the same orbital character that may lead to unfavorably high electron–hole recombination rates. Another limitation of iron(II) oxide is that the calculated valence band edge is not positioned well for oxidizing water. We predict that key properties, including band gaps, band edge positions, and possibly electron–hole recombination rates, may be improved by alloying TMOs that have different band alignments. A new metric, the band gap center offset, is introduced for simple screening of potential parent materials. The concept is illustrated by calculating the electronic structure of binary oxide alloys that contain manganese, nickel, iron, zinc, and/or magnesium, within density functional theory (DFT)+U and hybrid DFT theories. We conclude that alloys of iron(II) oxide are worth evaluating further as solar energy conversion materials.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

Ab Initio Study of Atomic and Electronic Structure of Promising Ba4XMn3O12 (X = Nb, Ce, Pr) Oxides for Solar Thermochemical Hydrogen Production

The two-step metal oxide water-splitting cycle is one of the most viable approach for Solar Thermochemical Hydrogen (STCH) production. Challenges exist in finding suitable oxides that can satisfy thermodynamics of the STCH redox cycle under viable range of temperatures and partial pressures. Recently, BXM family members, i.e., Ba4NbMn3O12 (BNM), Ba4CeMn3O12 (BCM), Ba4PrMn3O12 (BPM) are discovered to exhibit promising STCH performance. However, the magnetic degrees of freedom of their experimental crystal structures is not characterized, and only hypothetical models exist for their electronic structure. We performed Monte-Carlo sampling for the magnetic spin arrangement of Mn atoms to provide explicit atomic structure models for their ground state 12R polytype and determined the most stable spin configuration for each member after structure relaxation using density functional theory (DFT) calculations. We also elucidate the most stable charge configuration (Mn3+/Mn4+ arrangement) for BNM among the existing hypothesis in literature. We investigate these strongly correlated oxides using different levels of theory (DFT+U, Hybrid-DFT) to develop better understanding of their electronic structure. These calculations allowed us to develop a model based on molecular orbital interactions that help explain the observed changes in their experimental x-ray spectroscopy measurements. Thereby, help link differences in electronic structure of BXM family members to their varying water-splitting behavior. These structure models will further facilitate future in-depth defect studies to model STCH redox cycle of these oxides.

atomic and magnetic structure↗
DOE OSTI2016

Does DFT+U mimic hybrid density functionals?

Here, this work examines the question of how a Hubbard U correction to a local exchange–correlation functional compares with adding Hartree–Fock exchange to a local functional for both solid-state and molecular properties. We compute a solid-state property, namely the band gap, and thermochemical molecular properties, in particular main-group bond energies, transition-metal–ligand bond energies, and barrier heights, to elucidate whether the DFT+U method mimics hybrid DFT. We find that a calculation with a Hubbard U correction may or may not mimic a hybrid functional – depending on the atom, the subshell, and the property to which it is applied. For band gaps, we find that adding a Hubbard U correction to the valence d orbitals of transition metals increases the band gap, which thereby gets closer to the experimental value, while adding a Hubbard U correction to valence s or p orbitals of main group elements need not always increase the band gap. For molecular thermochemistry, we find that adding a Hubbard U correction to a local density functional need not have the same effect as adding Hartree–Fock exchange to a local density functional. For example when compared to a local DFT, hybrid DFT increases the barrier height in all cases, but DFT+U does not always increase the barrier height. For the band gaps of transition metal monoxides, the Hubbard-corrected results lowered the mean errors significantly and were comparable to what could be achieved with a much more expensive hybrid functional, but for reaction barrier heights and bond energies the Hubbard correction can lower the mean error by approximately a kcal/mol. As part of the analysis, we also compare VASP and Gaussian 09 calculations for the same density functional.

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

Communication: On the stability of ice 0, ice i, and I h

Using ab initio methods, we examine the stability of ice 0, a recently proposed tetragonal form of ice implicated in the homogeneous freezing of water [J. Russo, F. Romano, and H. Tanaka, Nat. Mater. 13, 670 (2014)]. Vibrational frequencies are computed across the complete Brillouin Zone using Density Functional Theory (DFT), to confirm mechanical stability and quantify the free energy of ice 0 relative to ice I h . The robustness of this result is tested via dispersion corrected semi-local and hybrid DFT, and Quantum Monte-Carlo calculation of lattice energies. Results indicate that popular molecular models only slightly overestimate the stability of ice zero. In addition, we study all possible realisations of proton disorder within the ice zero unit cell, and identify the ground state as ferroelectric. Comparisons are made to other low density metastable forms of ice, suggesting that the ice i structure [C. J. Fennel and J. D. Gezelter, J. Chem. Theory Comput. 1, 662 (2005)] may be equally relevant to ice formation.

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

Origin of Pronounced Nonlinear Band Gap Behavior in Lead–Tin Hybrid Perovskite Alloys

Mixed lead-tin hybrid perovskite alloy CH 3 NH 3 (Pb 1-x Sn x )I 3 attracted significant attention lately because of the reduction of its band gap below both end compounds, which makes it a promising bottom cell material in all-perovskite tandem solar cells. The effect is a consequence of a strongly nonlinear dependence of the alloy band gap on chemical composition. Here, we use electronic structure calculations at different levels of theory (density functional theory (DFT), hybrid DFT, and QSGW, with and without spin-orbit interactions) to investigate the presently elusive origin of this effect. Contrary to current conflicting studies, our results show that neither spin-orbit interactions nor the composition induced changes of the crystal structure and ordering of atoms contributes to the nonlinearity of the band gap. We find that the strong nonlinearity is primarily a consequence of chemical effects, i.e., the mismatch in energy between s and p atomic orbitals of Pb and Sn, which form the band edges of the alloy. These results unravel the nature of the band gap bowing in Sn/Pb hybrid perovskite alloys and offer a relatively simple way to estimate evolution of the band gap in other hybrid perovskite alloys.

14 SOLAR ENERGY↗