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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
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DOE OSTI2024

Discovery of Stable Surfaces with Extreme Work Functions by High‐Throughput Density Functional Theory and Machine Learning

Abstract The work function is the key surface property that determines the energy required to extract an electron from the surface of a material. This property is crucial for thermionic energy conversion, band alignment in heterostructures, and electron emission devices. This work presents a high‐throughput workflow using density functional theory (DFT) to calculate the work function and cleavage energy of 33,631 slabs (58,332 work functions) that are created from 3,716 bulk materials. The number of calculated surface properties surpasses the previously largest database by a factor of ≈27. Several surfaces with an ultra‐low (<2 eV) and ultra‐high (>7 eV) work function are identified. Specifically, the (100)‐Ba‐O surface of BaMoO 3 and the (001)‐F surface of Ag 2 F have record‐low (1.25 eV) and record‐high (9.06 eV) steady‐state work functions. Based on this database a physics‐based approach to featurize surfaces is utilized to predict the work function. The random forest model achieves a test mean absolute error (MAE) of 0.09 eV, comparable to the accuracy of DFT. This surrogate model enables rapid predictions of the work function (≈ 10 5 faster than DFT) across a vast chemical space and facilitates the discovery of material surfaces with extreme work functions for energy conversion and electronic device applications.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2013

Function space requirements for the single-electron functions within the multiparticle Schroedinger equation

Our previously described method to approximate the many-electron wavefunction in the multiparticle Schroedinger equation reduces this problem to operations on many single-electron functions. In this work, we analyze these operations to determine which function spaces are appropriate for various intermediate functions in order to bound the output. This knowledge then allows us to choose the function spaces in which to control the error of a numerical method for single-electron functions. We find that an efficient choice is to maintain the single-electron functions in L{sup 2} Intersection L{sup 4}, the product of these functions in L{sup 1} Intersection L{sup 2}, the Poisson kernel applied to the product in L{sup 4}, a function times the Poisson kernel applied to the product in L{sup 2}, and the nuclear potential times a function in L{sup 4/3}. Due to the integral operator formulation, we do not require differentiability.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2010

Combining density-functional theory and density-matrix-functional theory

We combine density-functional theory with density-matrix-functional theory to draw the best from both worlds. This is achieved by range separation of the electronic interaction which permits one to rigorously combine a short-range density functional with a long-range density-matrix functional. The short-range density functional is approximated by the short-range version of the Perdew-Burke-Ernzerhof functional (srPBE). The long-range density-matrix functional is approximated by the long-range version of the Buijse-Baerends functional (lrBB). The obtained srPBE+lrBB method accurately describes both the static and dynamic electron correlation at a computational cost similar to that of standard density-functional approximations. This is shown for the dissociation curves of the H{sub 2}, LiH, BH, and HF molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2010

Binding Energy of d¹º Transition Metals to Alkenes By Wave Function Theory and Density Functional Theory

The structures of Pd(PH₃)₂ and Pt(PH₃)₂ complexes with ethene and conjugated CnH n+2 systems (n=4, 6, 8, and 10) were studied. Their binding energies were calculated using both wave function theory (WFT) and density functional theory (DFT). Previously it was reported that the binding energy of the alkene to the transition metal does not depend strongly on the size of the conjugated C n H n+2 ligand, but that DFT methods systematically underestimate the binding energy more and more significantly as the size of the conjugated system is increased. Our results show that recently developed density functionals predict the binding energy for these systems much more accurately. New benchmark calculations carried out by the coupled cluster method based on Brueckner orbitals with double excitations and a quasiperturbative treatment of connected triple excitations (BCCD(T)) with a very large basis set agree even better with the DFT predictions than do the previous best estimates. The mean unsigned error in absolute and relative binding energies of the alkene ligands to Pd(PH₃)₂ is 2.5 kcal/mol for the ωB97 and M06 density functionals and 2.9 kcal/mol for the M06-L functional. Adding molecular mechanical damped dispersion yields even smaller mean unsigned errors: 1.3 kcal/mol for the M06-D functional, 1.5 kcal/mol for M06- L-D, and 1.8 kcal/mol for B97-D and ωB97X-D. The new functionals also lead to improved accuracy for the analogous Pt complexes. These results show that recently developed density functionals may be very useful for studying catalytic systems involving Pd d¹º centers and alkenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Covariant spectator theory of np scattering: Effective range expansions and relativistic deuteron wave functions

We present the effective range expansions for the {sup 1}S{sub 0} and {sup 3}S{sub 1} scattering phase shifts, and the relativistic deuteron wave functions that accompany our recent high precision fits (with {chi}{sup 2}/N{sub data{approx_equal}}1) to the 2007 world np data below 350 MeV. The wave functions are expanded in a series of analytical functions (with the correct asymptotic behavior at both large and small arguments) that can be Fourier-transformed from momentum to coordinate space and are convenient to use in any application. A fortran subroutine to compute these wave functions can be obtained from the authors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Hexagon functions and the three-loop remainder function

We present the three-loop remainder function, which describes the scattering of six gluons in the maximally-helicity-violating configuration in planar NN = 4 super-Yang-Mills theory, as a function of the three dual conformal cross ratios. The result can be expressed in terms of multiple Goncharov polylogarithms. We also employ a more restricted class of hexagon functions which have the correct branch cuts and certain other restrictions on their symbols. We classify all the hexagon functions through transcendental weight five, using the coproduct for their Hopf algebra iteratively, which amounts to a set of first-order differential equations. The three-loop remainder function is a particular weight-six hexagon function, whose symbol was determined previously. The differential equations can be integrated numerically for generic values of the cross ratios, or analytically in certain kinematic limits, including the near-collinear and multi-Regge limits. These limits allow us to impose constraints from the operator product expansion and multi-Regge factorization directly at the function level, and thereby to fix uniquely a set of Riemann ζ valued constants that could not be fixed at the level of the symbol. The near-collinear limits agree precisely with recent predictions by Basso, Sever and Vieira based on integrability. The multi-Regge limits agree with the factorization formula of Fadin and Lipatov, and determine three constants entering the impact factor at this order. We plot the three-loop remainder function for various slices of the Euclidean region of positive cross ratios, and compare it to the two-loop one. For large ranges of the cross ratios, the ratio of the three-loop to the two-loop remainder function is relatively constant, and close to -7.

extended supersymmetry↗
DOE OSTI2021

Examination of How Well Long-Range-Corrected Density Functionals Satisfy the Ionization Energy Theorem

For this work, we calculated the vertical ionization energies (VIE) of 99 species in two ways to examine the accuracy of several long-range-corrected (LC) hybrid meta functionals in comparison with a gradient approximation (GA), global hybrids, and doubly hybrids. In the category of LC functionals, we examined both those with meta ingredients (i.e., that depend on the kinetic energy density) and those without them. The LC-hybrid meta functionals examined are M11, revM11, M11plus, and ωB97M-V. The reference data used to assess accuracy consist of 95 molecules and 4 atoms in the GW100 set. The two methods studied are the ΔSCF method (involving the difference of neutral and cation self-consistent field (SCF) energies) and the ionization energy theorem (involving the orbital energy of the highest occupied molecular orbital, HOMO). We calculated linear correlation coefficients (r 2 ) and mean absolute deviations (MADs) between each approach and the reference VIE value from the CCSD(T)/def2-TZVPP level of theory. We compared the new LC-hybrid meta calculations to calculations with the 10 functionals in a previous VIE study by Brémond et al. and to the calculations with LC-BLYP (LC-Becke, Lee–Yang–Parr), CAM-B3LYP (Coulomb-attenuating-method Becke-3-parameter Lee–Yang–Parr), LC-ωHPBE, and ωB97X-D. The results show that Minnesota LC-hybrid meta functionals have the smallest mean absolute deviation of ionization energy theorem VIEs with the reference data; the LC-ωHPBE functional also does quite well in this test. This is very encouraging and indicates that LC-hybrid meta functionals would be the best starting points for the tuning strategy that has been shown to be a very good procedure for improving time-dependent density functional calculations, and it also helps explain the good success of LC-hybrid meta functionals for molecular excitation energies.

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

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B{sub 3}N{sub 3}H{sub 6}) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

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

Generalized gradient approximation exchange energy functional with correct asymptotic behavior of the corresponding potential

A new non-empirical exchange energy functional of the generalized gradient approximation (GGA) type, which gives an exchange potential with the correct asymptotic behavior, is developed and explored. In combination with the Perdew-Burke-Ernzerhof (PBE) correlation energy functional, the new CAP-PBE (CAP stands for correct asymptotic potential) exchange-correlation functional gives heats of formation, ionization potentials, electron affinities, proton affinities, binding energies of weakly interacting systems, barrier heights for hydrogen and non-hydrogen transfer reactions, bond distances, and harmonic frequencies on standard test sets that are fully competitive with those obtained from other GGA-type functionals that do not have the correct asymptotic exchange potential behavior. Distinct from them, the new functional provides important improvements in quantities dependent upon response functions, e.g., static and dynamic polarizabilities and hyperpolarizabilities. CAP combined with the Lee-Yang-Parr correlation functional gives roughly equivalent results. Consideration of the computed dynamical polarizabilities in the context of the broad spectrum of other properties considered tips the balance to the non-empirical CAP-PBE combination. Intriguingly, these improvements arise primarily from improvements in the highest occupied and lowest unoccupied molecular orbitals, and not from shifts in the associated eigenvalues. Those eigenvalues do not change dramatically with respect to eigenvalues from other GGA-type functionals that do not provide the correct asymptotic behavior of the potential. Unexpected behavior of the potential at intermediate distances from the nucleus explains this unexpected result and indicates a clear route for improvement.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Size-dependent error of the density functional theory ionization potential in vacuum and solution

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potential for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. In vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.

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

Local and linear chemical reactivity response functions at finite temperature in density functional theory

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

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

Shrinking Self-Interaction Errors with the Fermi–Löwdin Orbital Self-Interaction-Corrected Density Functional Approximation

The self-interaction error (SIE) is one of the major drawbacks of practical exchange-correlation functionals for Kohn-Sham density functional theory. Despite this, the use of methods that explicitly remove SIE from approximate density functionals is scarce in the literature due to their relatively high computational cost and lack of consistent improvement over standard modern functionals. Here, we assess the performance of a novel approach recently proposed by Pederson, Ruzsinszky, and Perdew for performing self-interaction free calculations in density functional theory based on Fermi-orbitals. To this end, we employ test sets consisting of reaction energies that are considered particularly sensitive to SIE. We found that the parameter-free Fermi-Löwdin orbital self-interaction correction method combined with standard local spin density approximation (LSDA) and Perdew-Burke-Ernzerhof (PBE) functionals gives a much better estimate of reaction energies compared to their parent LSDA and PBE functionals for most of the reactions in these two sets. They also perform on par with the global PBE0 and range-separated LC-ωPBE hybrids, which partially eliminate the SIE by including Hartree-Fock exchange. This shows the potential of the Fermi-Löwdin orbital self-interaction corrected (FLOSIC) method for practical density functional calculations without SIE.

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

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Zhou, Jiahua↗
DOE OSTI2015

Fragment approach to constrained density functional theory calculations using Daubechies wavelets

In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.

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

Density functional theory of water with the machine-learned DM21 functional

The delicate interplay between functional-driven and density-driven errors in density functional theory (DFT) has hindered traditional density functional approximations (DFAs) from providing an accurate description of water for over 30 years. Recently, the deep-learned DeepMind 21 (DM21) functional has been shown to overcome the limitations of traditional DFAs as it is free of delocalization error. To determine if DM21 can enable a molecular-level description of the physical properties of aqueous systems within Kohn–Sham DFT, we assess the accuracy of the DM21 functional for neutral, protonated, and deprotonated water clusters. Furthermore, we find that the ability of DM21 to accurately predict the energetics of aqueous clusters varies significantly with cluster size. Additionally, we introduce the many-body MB-DM21 potential derived from DM21 data within the many-body expansion of the energy and use it in simulations of liquid water as a function of temperature at ambient pressure. We find that size-dependent functional-driven errors identified in the analysis of the energetics of small clusters calculated with the DM21 functional result in the MB-DM21 potential systematically overestimating the hydrogen-bond strength and, consequently, predicting a more ice-like local structure of water at room temperature.

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

Deconstructing the Soil Microbiome into Reduced-Complexity Functional Modules

The soil microbiome is an invaluable component of the biosphere and critical for ecosystem functions, including biogeochemical cycling, soil-atmosphere gas exchange, degradation of toxic compounds, and promotion of plant growth and stress resistance/resilience. An improved understanding of the soil microbiome will help with predicting how these processes respond to external perturbations, and with harnessing beneficial aspects of the soil microbiome for agronomic applications such as crop amendments. However, the extensive taxonomic and functional diversity inherent within the soil microbiome hinders efficient analysis of this system. Microbial biodiversity in soils is orders of magnitude greater than other commonly studied systems such as the human gut microbiome (Blum, Zechmeister-Boltenstern, and Keiblinger 2019; Berendsen, Pieterse, and Bakker 2012). Thousands of microbial taxa may be found in a single gram of soil (Roesch et al. 2007), and high rates of gene flow and mutation further promote microbial diversification (Sergaki et al. 2018). Concomitantly, functional diversity in soil is similarly extensive. Soil is a heterogeneous mixture of microenvironments with defined physical and chemical attributes (Bach et al. 2018), within which numerous microbial guilds of distinct life-strategies and metabolic capacities can be found (Perez-Garcia, Lear, and Singhal 2016; H.-S. Song et al. 2014). Furthermore, the soil microbiome harbors a significant fraction of rare and/or quiescent members (Blagodatskaya and Kuzyakov 2013) that exist below the threshold of detection of current technologies. Such rare taxa may make significant contributions to process rates (Shade and Gilbert 2015; Dawson et al. 2017), but their scarcity complicates their identification and analysis. Finally, the vast amounts of information generated through holistic analyses of soil communities represent an intense computational burden (Scholz, Lo, and Chain 2012; Prosser 2015) that precludes assessment of the complete functional and taxonomic diversity contained in this ecosystem.

Naylor, Dan T.↗