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At least 415 records · Page 23

Dynamical structure factors of warm dense matter from time-dependent orbital-free and mixed-stochastic-deterministic density functional theory

Abstract We present the first calculations of the inelastic part of the dynamical structure factor (DSF) for warm dense matter (WDM) using time-dependent orbital-free density functional theory (TD-OF-DFT) and mixed-stochastic-deterministic (mixed) Kohn Sham TD-DFT (KS TD-DFT). WDM is an intermediate phase of matter found in planetary cores and laser-driven experiments, where the accurate calculation of the DSF is critical for interpreting x-ray Thomson scattering measurements. Traditional TD-DFT methods, while highly accurate, are computationally expensive, motivating the exploration of TD-OF-DFT and mixed TD-KS-DFT as more efficient alternatives. We applied these methods to experimentally measured WDM systems, including solid-density aluminum and beryllium, compressed beryllium, and carbon–hydrogen mixtures. Our results show that TD-OF-DFT requires a dynamical kinetic energy potential in order to qualitatively capture the plasmon response. Additionally, it struggles with capturing bound electron contributions. In contrast, mixed TD-KS-DFT offers greater accuracy in distinguishing bound and free electron effects, aligning well with experimental data, though at a higher computational cost. This study highlights the trade-offs between computational efficiency and accuracy, demonstrating that TD-OF-DFT remains a valuable tool for rapid scans of parameter space, while mixed TD-KS-DFT should be preferred for high-fidelity simulations. Our findings provide insight into the future development of DFT methods for WDM and suggest potential improvements for TD-OF-DFT.

36 MATERIALS SCIENCE↗

Radionuclide incorporation in negative thermal expansion α-Zr(WO 4 ) 2 : A density functional theory study

The incorporation of uranium, plutonium and technetium in the negative thermal expansion (NTE) α-Zr (WO 4 ) 2 has been investigated within the framework of density functional theory (DFT). It is found that the vacancy formation energies of the charged vacancies are overall larger than that of its counterpart neutral Frenkel defects and Schottky defects. DFT calculations suggest that U and Pu substitutions for the Zr site are preferred in α-Zr (WO 4 ) 2 . In case of Tc substitution, both Tc(IV) for the Zr site and Tc(VII) for the W site are considered under oxygen-poor and oxygen-rich conditions, while Tc(VII) substitution can be improved significantly by including Y 2 O 3 (charge compensation).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward a better understanding of Ni coarsening in solid oxide cells: NiH on Ni (111) examined at the level of density-functional theory (and KMC)

Ni coarsening in the fuel electrode of solid oxide cells (SOCs) is known to be significantly faster under a humid atmosphere. In this talk, density-functional theory and kinetic Monte Carlo methods are used to explore the hypothesis that the surface diffusion of NiH on Ni may promote Ni coarsening in the SOC operated in electrolysis cell mode. Defining the surface diffusivity as the product of the fractional surface coverage and single-molecule surface diffusivity, the surface diffusivity of NiH on Ni (111) is found to be large enough under a significant overpotential to support the above hypothesis. However, as NiH could dissociate on Ni (111), more work is needed to show that NiH may promote Ni coarsening.

Mantz, Yves↗

Modal density function and number of propagating modes in ducts

The question of the number of propagating modes within a small range of mode cut off ratio was raised. The population density of modes were shown to be greatest near cut off and least for the well propagating modes. It was shown that modes of nearly the same cut off ratio behave nearly the same in a sound absorbing duct as well as in the way they propagate to the far. Handling all of the propagating modes individually, they can be grouped into several cut off ratio ranges. It is important to know the modal density function to estimate acoustic power distribution.

Rice, E. J.↗

Linear Scaling Density Functional Calculations with Gaussian Orbitals

Recent advances in linear scaling algorithms that circumvent the computational bottlenecks of large-scale electronic structure simulations make it possible to carry out density functional calculations with Gaussian orbitals on molecules containing more than 1000 atoms and 15000 basis functions using current workstations and personal computers. This paper discusses the recent theoretical developments that have led to these advances and demonstrates in a series of benchmark calculations the present capabilities of state-of-the-art computational quantum chemistry programs for the prediction of molecular structure and properties.

Scuseria, Gustavo E.↗

Irreversible oxygen poisoning: Modeling the initial water dissociation kinetics on δ-Pu(111) and δ-Pu(100) through density functional theory

In this work, the initial kinetics of water dissociation on two facets of δ-plutonium, δ-Pu(111) and δ-Pu(100), are explored through density functional theory in order to understand how water dissociation occurs on these facets. We explored the dissociation of water via the formation of hydroxyls, atomic hydrogen, and atomic oxygen species on each facet. We calculate low energetic barriers for water to split to adsorbed hydrogen and hydroxyl species at 0.19 eV for δ-Pu(111) and 0.07 eV for δ-Pu(100). The hydroxyl has a barrier of 0.64 and 0.37 eV to cleave the hydrogen–oxygen bond on δ-Pu(111) and δ-Pu(100), respectively. Due to the highly exergonic adsorption free energy of atomic oxygen of −2.10 eV, the metallic surfaces are found to be fully covered in oxygen, even with the inclusion of oxygen lateral interactions. When combined with the reaction thermodynamics, this free energy of adsorption forms a molecular oxygen desorption barrier greater than 9.51 eV (918 kJ/mol). These results, combined with simulated temperature programed desorption spectra, indicate that oxygen formed via water dissociation on δ-Pu (111) and (100) facets induces an irreversible poison that prevents further reaction of water directly on metallic plutonium surfaces, most likely due to the strong hybridization of the Pu and O valence states. Therefore, these results imply that another mechanism is responsible for the continuously experimentally measured water dissociation, which is most likely due to the Pu oxide.

36 MATERIALS SCIENCE↗

Investigation of estimators of probability density functions

Four research projects are summarized which include: (1) the generation of random numbers on the IBM 360/44, (2) statistical tests used to check out random number generators, (3) Specht density estimators, and (4) use of estimators of probability density functions in analyzing large amounts of data.

Speed, F. M.↗

Molecular Structure and Electron Affinity of Metal-Solvent Complexes: Insights from Density Functional Theory Simulations

A molecular level understanding of the structure and energetics of the monovalent and divalent metal ion complexes is of great importance for development of next-generation batteries. Here, Density Functional Theory (DFT) simulations at the ωb97xD/6-31 + G(d,p) level of theory are performed to investigate the interaction of metal ions (Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ ) with 26 organic solvent molecules. The reduction energetics (electron affinity and reduction potential) and structural responses of the solvent molecules and the molecular complexes are discussed. The DFT calculations are carried out to investigate the structure, energetics and electron affinities of chelated complexes of water (H 2 O), tetrahydrofuran (THF) and di-methoxy ethane (DME) solvent molecules. Additionally, ab initio dynamic simulations (AIMD) at 298 K using atom centered density matrix propagation (ADMP) formalism are performed to understand the spontaneous structure formation upon electron attachment of the metal ion-solvent complexes. The ADMP simulations indicate the decomposition of Mg + -(DME) 3 complex via cleavage of C–O bond of one of the three DME molecules indicating irreversible decomposition of DME in the presence of the Mg + radical. We believe that the data collected as part of this investigation serves as a library of fundamental knowledge towards a deeper understanding of the electrode-electrolyte interfacial reactions.

25 ENERGY STORAGE↗

Parallel transport dynamics for mixed quantum states with applications to time-dependent density functional theory

Direct simulation of the von Neumann dynamics for a general (pure or mixed) quantum state can often be expensive. One prominent example is the real-time time-dependent density functional theory (rt-TDDFT), a widely used framework for the first principle description of many-electron dynamics in chemical and materials systems. Practical rt-TDDFT calculations often avoid the direct simulation of the von Neumann equation, and solve instead a set of Schrödinger equations, of which the dynamics is equivalent to that of the von Neumann equation. However, the time step size employed by the Schrödinger dynamics is often much smaller. Here, in order to improve the time step size and the overall efficiency of the simulation, we generalize a recent work of the parallel transport (PT) dynamics for simulating pure states [An, Lin, Multiscale Model. Simul. 18, 612, 2020] to general quantum states. The PT dynamics provides the optimal gauge choice, and can employ a time step size comparable to that of the von Neumann dynamics. Going beyond the linear and near adiabatic regime in previous studies, we find that the error of the PT dynamics can be bounded by certain commutators between Hamiltonians, density matrices, and their derived quantities. Such a commutator structure is not present in the Schrödinger dynamics. We demonstrate that the parallel transport-implicit midpoint (PT-IM) method is a suitable method for simulating the PT dynamics, especially when the spectral radius of the Hamiltonian is large. The commutator structure of the error bound, and numerical results for model rt-TDDFT calculations in both linear and nonlinear regimes, confirm the advantage of the PT dynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Crystal growth, density functional theory, and scintillation properties of Tl 3 LnCl 6 :Ce 3+ and TlLn 2 Cl 7 :Ce 3+ (Ln = Y, Gd)

In this paper we report on the crystal growth, density functional theory (DFT) calculations and scintillation properties of Tl 3 LnCl 6 :Ce and TlLn 2 Cl 7 :Ce(Ln = Y, Gd). Crystals were grown by the Vertical Bridgman technique up to 16 mm in diameter and 25 mm long. Crystals of Tl 3 YCl 6 :Ce and Tl 3 GdCl 6 :Ce belong to the family of the Nesohalides which have the monoclinic crystal structure. Crystals of TlY 2 Cl 7 :Ce and TlGd 2 Cl 7 :Ce belong to the family of the Phyllohalides which have either the monoclinic or the orthorhombic crystal structure. We report the light yields of these Nesohalides and Phyllohalides are typically on the order of 35,000–40,000 ph/MeV.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A strain density function to analyze particle size effects during high velocity impacts of yttria

Here, the impact behavior of a single yttria (Y 2 O 3 ) nanoparticle onto a Y 2 O 3 substrate is studied as a function of particle velocity (300–1200 m/s) and diameter (12–50 nm) using molecular dynamics simulations. To analyze the results, a strain density function is developed to provide both quantitative and qualitative information about the deformation mechanisms that contribute to the final state of the system. This function provides both clear evidence of shear localization and insight into the conditions for which localization occurs during the impact of Y 2 O 3 particles as they approach experimentally relevant sizes. Further analysis shows that localization and fragmentation only occur for Y 2 O 3 impacts with diameters of at least 50 nm, while particles with diameters of 25 nm and smaller deform primarily by amorphization and viscous flow. Implications for the deposition of films of Y 2 O 3 and other rare-earth oxides via the micro cold spray process are discussed.

36 MATERIALS SCIENCE↗

Activation, Dehydrogenation, and Carbon–Carbon Coupling of Methane by Iridium Cations Studied by Infrared Multiple Photon Dissociation Spectroscopy and Density Functional Theory

Products resulting from the sequential activation of one, two, three, and four methane molecules by atomic iridium cations were characterized by gas-phase infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. Iridium cations were generated using a laser ablation source and reacted with methane in a linear radiofrequency ion trap before mass analysis and spectroscopic interrogation in a Fourier transform ion cyclotron resonance mass spectrometer coupled to the free-electron laser for intracavity experiments (FELICE) beamline. Product ions were irradiated using infrared light over the 250–1500 cm –1 range. Comparisons between the experimental and DFT-calculated spectra enabled structural determination of the products formed. The observed products include HIrCH + , Ir(CH 2 ) 2 + , H s Ir(C 3 H 5 ) + , and Ir(CH 3 ) s (C 3 H 5 ) + , where the subscript s denotes a syn orientation of the two ligands. Furthermore, formation of the latter two products provides evidence for efficient C–H bond activation and subsequent C–C coupling on the atomic iridium cation.

Chemical reactions↗

Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Boron suboxide (B 6 O) is a boron-rich compound derived from the α-rhombohedral boron lattice with extreme hardness and unusual semiconducting properties. In this work, density functional theory (DFT) was used to show that unit cell volume, mechanical strength, band gaps, and thermodynamic stabilities of B 6 O were influenced by the interstitial elements and point defects at the icosahedral sites. While the hexagonal unit cell volume (HUCV) varies with interstitial occupancy, it is the icosahedral defect that weakens the intrinsic bulk modulus of B 6 O. Using the hybrid HSE functional, we confirmed that the perfect B 6 O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. The formation free energies calculated over a wide range of temperatures (0–2500 K) and pressures (0–80 GPa) predict that formations of interstitial defects become favorable only at higher temperatures (ca. 1800 K) in bulk B 6 O lattices. The nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barrier of 0.16 eV. More complex B diffusion paths involving the reorganization of icosahedral boron atoms incur higher barriers (>1 eV). In contrast, the diffusion of interstitial O atoms is facile with a barrier of 0.4 eV. Lastly, successive O insertions into the α-B lattice were performed using DFT to generate a basic understanding of the oxidation process. Furthermore, these calculations provide fundamental atomistic insights into the growth of B 6 O crystals and control of their point defects.

36 MATERIALS SCIENCE↗

Time Dependent Density Functional Theory Calculations of Large Compact PAH Cations: Implications for the Diffuse Interstellar Bands

We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcoronene, the largest species containing more than 50 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.

Weisman, Jennifer L.↗

Two-temperature warm dense hydrogen as a test of quantum protons driven by orbital-free density functional theory electronic forces

We consider a steady-state (but transient) situation in which a warm dense aggregate is a two-temperature system with equilibrium electrons at temperature Te, ions at Ti, and Te ≠ Ti. Such states are achievable by pump–probe experiments. For warm dense hydrogen in such a two-temperature situation, we investigate nuclear quantum effects (NQEs) on structure and thermodynamic properties, thereby delineating the limitations of ordinary ab initio molecular dynamics. We use path integral molecular dynamics (PIMD) simulations driven by orbital-free density functional theory (OFDFT) calculations with state-of-the-art noninteracting free-energy and exchange-correlation functionals for the explicit temperature dependence. We calibrate the OFDFT calculations against conventional (explicit orbitals) Kohn–Sham DFT. We find that when the ratio of the ionic thermal de Broglie wavelength to the mean interionic distance is larger than about 0.30, the ionic radial distribution function is meaningfully affected by the inclusion of NQEs. Moreover, NQEs induce a substantial increase in both the ionic and electronic pressures. This confirms the importance of NQEs for highly accurate equation-of-state data on highly driven hydrogen. For Te > 20 kK, increasing Te in the warm dense hydrogen has slight effects on the ionic radial distribution function and equation of state in the range of densities considered. In addition, we confirm that compared with thermostatted ring-polymer molecular dynamics, the primitive PIMD algorithm overestimates electronic pressures, a consequence of the overly localized ionic description from the primitive scheme.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A noncollinear density functional theory ansatz for the phononic and thermodynamic properties of α -Pu

Plutonium's phase diagram is host to complex structures and interactions that make the description of its ground state properties elusive. Using all-electron density functional theory calculations, we study the thermodynamic properties of α-Pu. To do this, we build on recent work in the literature by introducing a novel noncollinear magnetic ansatz for α-Pu's ground state. We show that the noncollinear ansatz improves the description of the experimental phonon density of states, heat capacity, and thermal expansion over previous results obtained with a collinear ansatz. Here, despite lacking a bond-equivalent picture of the bonding, these new results for α-Pu, along with recent results on δ-Pu, demonstrate the efficacy of noncollinear ansatzes for the description of plutonium.

36 MATERIALS SCIENCE↗

The Good, the Bad, and the Ugly: Pseudopotential Inconsistency Errors in Molecular Applications of Density Functional Theory

The pseudopotential (PP) approximation is one of the most common techniques in computational chemistry. Despite its long history, the development of custom PPs has not tracked with the explosion of different density functional approximations (DFAs). As a result, the use of PPs with exchange/correlation models for which they were not developed is widespread, although this practice is known to be theoretically unsound. The extent of PP inconsistency errors (PPIEs) associated with this practice has not been systematically explored across the types of energy differences commonly evaluated in chemical applications. Here, we evaluate PPIEs for a number of PPs and DFAs across 196 chemically relevant systems of both transition-metal and main-group elements, as represented by the W4-11, TMC34, and S22 data sets. Near the complete basis set limit, these PPs are found to cleanly approach all-electron (AE) results for noncovalent interactions but introduce root-mean-squared errors (RMSEs) upwards of 15 kcal mol –1 into predictions of covalent bond energies for a number of popular DFAs. We achieve significant improvements through the use of empirical atom- and DFA-specific PP corrections, indicating considerable systematicity of the PPIEs. The results of this work have implications for chemical modeling in both molecular contexts and for DFA design, which we discuss.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗