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At least 559 records · Page 31

First principles study of the stability and thermal conductivity of novel Li-Be hybrid ceramics

Hybrid Li-Be ceramics, combining both tritium (T) breeder (Li) and neutron multiplier (Be) for use as part of the fuel cycle of future nuclear fusion reactors are proposed. The development of such hybrid materials may reduce thermal gradients through better matching of thermal properties, mitigating the detrimental effects that may accompany traditional breeder systems while maintaining acceptable neutron multiplication and T breeding. Here, first-principles methods are used to investigate stability and thermal transport properties of a set of compounds containing both Li and Be. It is demonstrated that BeLi 2 O 4 Ge and BeLi 2 O 4 Si are mechanically stable and have formation energies comparable with leading candidates for solid state breeder materials, Li 2 TiO 3 , Li 2 ZrO 3 . It is also demonstrated that similar to the leading candidates, these compounds are insulators with thermal transport defined by phonons. The calculated thermal conductivity of BeLi 2 O 4 Ge is slightly higher compared to Li 2 TiO 3 or Li 2 ZrO 3 while in the BeLi 2 O 4 Si it is almost three times higher compared to the rest of compounds due to a higher phonon group velocities and increased phonon lifetimes. These results indicate that hybrid Li-Be ceramics offer a potential route towards better matching of thermal properties with minimal functional property degradation, thereby offering better overall fuel cycle performance.

36 MATERIALS SCIENCE↗

Pressure-induced phase transition of calcite and aragonite: A first principles study

The thermodynamic phase stabilities of calcite and aragonite have been investigated from lattice vibrational analyses based on first-principles calculations. Different pressure dependences in phonon feature were found between the two polymorphs, suggesting different physical origins of the pressure-induced phase transitions. In the most stable phase in calcite (calcite I), an imaginary phonon mode consisting of rotation of CO{sub 3} ions with slight displacement of Ca ions appears at the F point in the Brillouin zone above 0.8 GPa. Such a soft mode means that external pressure induces the lattice-dynamical instability of calcite I leading to the phase transition to calcite II. On the other hand, the origin of the phase transition in aragonite is not due to such a lattice-dynamical instability. The estimated thermodynamical properties indicate that a first-order phase transition occurs between aragonite and post-aragonite at 34.7 GPa, coinciding with the reported experimental value at room temperature (35 GPa).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

First principles Peierls-Boltzmann phonon thermal transport: A topical review

The advent of coupled thermal transport calculations with interatomic forces derived from density functional theory has ushered in a new era of fundamental microscopic insight into lattice thermal conductivity. Subsequently, significant new understanding of phonon transport behavior has been developed with these methods, and because they are parameter free and successfully benchmarked against a variety of systems, they also provide reliable predictions of thermal transport in systems for which little is known. This topical review will describe the foundation from which first principles Peierls-Boltzmann transport equation methods have been developed, and briefly describe important necessary ingredients for accurate calculations. Sample highlights of reported work will be presented to illustrate the capabilities and challenges of these techniques, and to demonstrate the suite of tools available, with an emphasis on thermal transport in micro- and nano-scale systems. In conclusion, future challenges and opportunities will be discussed, drawing attention to prospects for methods development and applications.

74 ATOMIC AND MOLECULAR PHYSICS↗

Transition Metal Oxides as Cathodes in Li-O2 battery: A First Principles Investigation

Li-O2 batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like Dimethyl ether (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of cathode and reduction of cyclability. In this work, we investigate some of the well-known oxides as cathodes with focus on the interface between the oxide surfaces and the discharge product: Li2O2, in the Li-O2 battery using first principles computations. Our results show that attention must be paid on choosing the appropriate surface of the oxides. We extend the analysis to suggest other possible oxide chemistries that should be investigated as cathodes in Li-O2 batteries.

Li-O2 battery↗

Crystal structure, energetics, and phase stability of strengthening precipitates in Mg alloys: A first-principles study

Magnesium alloys have attracted increasing interest due to their potential use as light-weight structural materials but their application is limited by their low strength compared to conventional alloys. Age hardening is commonly employed to form strengthening precipitates in such alloys, which impedes the motion of dislocations, and leads to improved strength. However, the exact composition, crystal structure, and energetics of many of these strengthening precipitates are either unknown or not clearly resolved, making the precise engineering and design of such alloys difficult. Toward this end, we use first-principles density functional theory calculations to elucidate the crystal structures and energetics of a very large set of precipitates in magnesium alloys. For cases where the precipitate crystal structure is not known, we comprehensively search over decorations of many prototype structures, including hcp superstructures, and in addition, perform global structural optimization using the Minima Hopping Method to predict suitable crystal structures. For all the strengthening precipitates, we calculate the formation energies, construct the respective zero temperature convex hulls, and analyze their stabilities. Here, we show that the bulk formation energies per solute atom (essentially, the solute chemical potentials) decrease along the observed sequences of precipitation, validating our calculations in Mg-{Nd, Gd, Y, Y-Nd, Nd-Zn, Gd-Zn, Y-Zn, Al, Zn, Sn, Al-Ca, Ca-Zn} alloy systems. In addition, we construct a monolayer model for the Guinier-Preston zones (GP zones) observed in the Mg-Nd-Zn system during early stages of age hardening, and thereby explain the formation of the γ" (Mg 5 (Nd,Zn)) phase from the GP zones, as observed in experiments.

36 MATERIALS SCIENCE↗

First-Principles Investigation of Half-Metallic Ferromagnetism of a New 1:1:1:1 Type Quaternary Heusler Compound YRhTiSi

First-principles theory was applied to study the electronic, magnetic, and half-metallic behaviors of a new Y-based equiatomic quaternary Heusler compound YRhTiSi. We will come to study the physical properties of this compound and find it has the half-metallic nature in the ferromagnetic (FM) state. The total magnetic moment of this compound YRhTiSi is 2 μ{sub B}, which follows the famous Slater-Pauling rule, Mt = Zt − 18, Mt is the total magnetic moment and Zt is the total number of valence electrons. Based on its equilibrium and strained lattice constants, the magnetic and half-metallic behaviors of this compound have been discussed in detail. And we find that the H–M gap and the band gap can be regulated through the effect of uniform strain and the tetragonal deformation. A large H–M gap of 0.48 eV has been found in our work, which is nearly larger than any previous study. Furthermore, the formation and cohesive energies have also been discussed in our work to examine the phase stability of YRhTiSi. This theoretical investigation provides further insight into the application of Y-based compounds as spintronic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First principles investigation of Ti adsorption and migration on Si(100) surfaces

The titanium adsorption on Si(100) is investigated using first principles computer modelling methods. Two new subsurface adsorption sites are described. They are located at the edge of the cavity topped by a surface silicon dimer. The migration of the titanium from the surface to the subsurface sites is facilitated when occurring via one of these sites. The ejection of one of the silicon atoms forming the surface dimer is also investigated. The actual step of the ejection requires more energy than previously thought although, when considering the global picture of a titanium atom on the surface leading to the ejection of a silicon atom, the overall rate is compensated by the facilitated migration of the titanium to the subsurface sites. The consecutive adsorption of a second and third titanium atom is also investigated. It is shown that titanium grows evenly on the surface in normal condition, showing no intermixing of the titanium and silicon beyond the silicon layer.

36 MATERIALS SCIENCE↗

Electronic structures and ferromagnetism of SnO{sub 2} (rutile) doped with double-impurities: First-principles calculations

The electronic and magnetic properties of double-impurities-doped SnO{sub 2} (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn{sub 1-2x}Cr{sub x}Mn{sub x}O2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μ{sub B} per supercell. The Cr-and Mn-doped SnO{sub 2} system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO{sub 2}, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO{sub 2}. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Uniaxial strain-induced magnetic order transition from E-type to A-type in orthorhombic YMnO{sub 3} from first-principles

The spin ordering magnetic structures of orthorhombic YMnO{sub 3} subjected to uniaxial strain have been investigated using first-principles calculations based on density functional theory. On applying compressive uniaxial strain of −0.8% along the b orientation, the spin ordering magnetic structure is predicted to change from E-type to A-type antiferromagnetic orderings. The structure analysis also reveals that the uniaxial strain has a dramatic influence on the Mn-O bond lengths and Mn-O-Mn bond angles, allowing the gradual suppression of the alternation of the long and short Mn-O-Mn bonds in the ab plane. These changes present very interesting possibilities for engineering the spin ordering along with ferroelectric property in orthorhombic YMnO{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On structural and lattice dynamic stability of LaF{sub 3} under high pressure: A first principle study

Structural and lattice dynamical stability of the LaF3 has been analyzed as a function of hydrostatic compression through first principle electronic band structure calculations. The comparison of enthalpies of various plausible structures calculated at various pressures suggests a phase transition from ambient condition tysonite structure (space group P-3c1) to a primitive orthorhombic structure (space group Pmmn) at a pressure of ∼19.5 GPa, in line with the experimental value of 16 GPa. Further, it is predicted that this phase will remain stable up to 100 GPa (the maximum pressure up to which calculations have been performed in the present work). The theoretically determined equation of state displays a good agreement with experimental data. Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state and compared with the available experimental data. Our lattice dynamic calculations correctly demonstrate that at zero pressure the tysonite structure is lattice dynamically stable whereas the Pmmn structure is unstable lattice dynamically. Further, at transition pressure the theoretically calculated phonon spectra clearly show that the Pmmn phase emerges as lattice dynamically stable phase whereas the tysonite structure becomes unstable dynamically, supporting our static lattice calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

First-principles studies of spin-phonon coupling in monolayer Cr 2 Ge 2 Te 6

Here, we perform systematic first-principles calculations to investigate the spin-phonon coupling (SPC) of Cr 2 Ge 2 Te 6 (CGT) monolayer (ML). It is found that the $E_g$ phonon mode at 211.8 cm –1 may have a SPC as large as 3.19 cm –1 , as it alters the direct exchange interaction across Cr-Cr pairs. The strength of SPC of the CGT ML can be decreased by an in-plane lattice stretch. These results provide useful insights for the understanding of SPC in two-dimensional magnetic semiconductors and may guide the design of spintronic and spin Seebeck materials and devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phase Switching as the Origin of Large Piezoelectric Response in Organic-Inorganic Perovskites: A First-Principles Study

Piezoelectrics are critical functional components of many practical applications such as sensors, ultrasonic transducers, actuators, medical imaging, telecommunications. So far, the best performing piezoelectrics are ferroelectric ceramics, many of which are toxic, heavy, hard, and cost-ineffective. Recently, a groundbreaking discovery of extraordinarily large piezoelectric coefficients in the family of organic-inorganic perovskites gave a hope for a cheaper, environmentally friendly, inexpensive, light-weight and flexible alternative. However, the origin of such response in organic-inorganic ferroelectrics whose spontaneous polarization is an order of magnitude smaller than for inorganic counterparts remains unclear. In this study we employ first-principles simulations to predict that the mechanism associated with large piezoelectric constants is of extrinsic origin and associated with switching between the stable phase and previously overlooked energetically competitive metastable phase that can be stabilized by the external stress. Here, the phase switching changes the polarization direction and, therefore, gives origin to large piezoelectric response, similar to PbZr$_{1-x}$Ti$_x$O$_3$ near morphotropic phase boundary. Existence of such metastable phases is likely to manifest as the dynamical molecular disorder above the Curie temperature and, therefore, could be intrinsic to the entire family of organic-inorganic ferroelectrics with such disorder.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A comprehensive first-principles study of solute elements in dilute Ni alloys: Diffusion coefficients and their implications to tailor creep rate

Diffusion regulates a vast number of materials properties and phenomena such as creep, the focus of the present work. However, a deep understanding of the effect of how each alloying element in a Ni-base superalloy affects properties such as diffusion and creep is far from complete. Here, in this study, we report temperature-dependent dilute solute diffusion coefficients and their implications to tailor the creep rate for 26 transition metal solute elements, X's, in fcc Ni using first-principles calculations. Calculations are performed using the five-frequency model for dilute solute diffusion and the nudged elastic band method within the local density approximation. Thermodynamic properties at finite temperatures for all configurations are calculated using the quasi-harmonic Debye model. In general, the fastest diffusing solute elements in Ni are found at the left side of the periodic table and the slowest diffusing solute elements are found in group VIIB. In particular, the present work indicates that the diffusivity of the dilute solute elements is correlated to the compressibility of each solute element on the respective Ni 31 X supercell, and not as strongly to the ionic radius of the solute elements, as previously suggested. Finally, results from the diffusivity study are combined with the previous results of elastic constants and stacking fault energies, and hence, a relative creep rate ratio for these 26 solute elements is modeled. It is shown that in most cases, slower diffusing solute elements provide the most creep resistance. This is true even at higher temperatures, due mainly to the solute's strong bonding with Ni atoms in the host lattice.

36 MATERIALS SCIENCE↗

First-principles comparative study of Cr migration in O3 and O/P hybrid-phased NaCrO 2

In layered Na transition-metal (TM) oxides, TM migration usually occurs at highly charged states and severely deteriorates the capacity and reversibility. Meanwhile, the formation of hybrid phases with the intergrowth of octahedral (O-type) and prismatic (P-type) Na layers also takes place at highly charged states. These hybrid phases are often more stable than simple O3 or P3 stackings. However, little is known about the mechanism and impact of TM migration in these hybrid phases. In this work, a comparative first-principles study is performed to understand the connections between structural changes and Cr migration in layered O3 and hybrid-phased NaCrO 2 . After Cr migration, the hybrid-phased NaCrO 2 suffers from greater layer shrinkage than the O3 phase. Three factors affect the Cr migration energy E mig : the Na concentration, local 3D configurations, and 2D in-plane geometries. Low Na concentrations and certain local 3D configurations facilitate the Cr migration. The Cr migration barriers in both O3 and hybrid-phased NaCrO 2 are positively correlated with the Cr E mig . The Cr migration in 17 doped O3 and hybrid-phased NaCrO 2 is surveyed. In these doped NaCrO 2 , a more uniform distribution of the Cr–O bond lengths usually suggests suppressed Cr migration. Optimal dopants for suppressing Cr migration are identified by considering E mig for both Cr and the dopant. Finally, our comparative study on Cr migration in O3 and hybrid-phased NaCrO 2 reveals the significant role of hybrid-phased structures in the development of layered cathode materials.

36 MATERIALS SCIENCE↗

Redox Defect Thermochemistry of FeAl 2 O 4 Hercynite in Water Splitting from First-Principles Methods

Solar thermochemical hydrogen (STCH) production is a promising route to produce fuels from sunlight via high-temperature water splitting. However, efficient and technologically viable implementations of this process only allow a narrow window of thermodynamic boundary conditions that can be used to cycle the system, thus limiting the design space for suitable metal oxide redox mediators. An oxygen defect redox mechanism can contribute a favorable reduction entropy to expand this window, and computational evaluation of materials with high oxygen defect entropies could play a pivotal role in guiding the discovery and design of suitable oxides. This study employs first-principles calculations to investigate the redox mediating defect mechanism of the STCH candidate material, hercynite (FeAl 2 O 4 ). We compare the results of total energy calculations from density functional theory (DFT) with beyond-DFT approaches, including hybrid functionals and the random phase approximation, which are among the most advanced methods currently feasible for supercell defect calculations. Using the predicted formation energies, we perform thermodynamic modeling of FeAl2O4 reduction and oxidation via free energy minimization that incorporates ideal gas, configurational, and vibrational entropy contributions evaluated within the quasi-harmonic approximation. Special attention is devoted to understanding interactions among co-existing defects, such as the association of pairs and complexes of O vacancies and cation antisite defects, and the effect of mutually compensating defect charges. Our results corroborate the notion that the details of defect interactions can be decisive for the viability of hydrogen production within the desirable STCH process window.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the roles of Cu- and Ag-deficient layers in chalcopyrite-based solar cells through first principles calculations

Chalcopyrites are a demonstrated material platform for realizing efficient thin-film photovoltaics, with the most well known Cu(In,Ga)Se 2 (CIGS)-based solar cells exceeding 23%. Several factors, including flexibility in tuning the absorber bandgap, enhanced surface treatments, and the electrically benign nature of common defects are responsible for the existing high performance and future promise in chalcopyrite-based photovoltaic devices. The introduction of Cu-poor phases (also known as ordered-vacancy compounds or OVCs) between the absorber and buffer layers in CIGS solar cells is known to enhance device performance; however, the overall properties and role of OVCs remain poorly understood. Using first principles calculations based on the density functional theory with screened hybrid functionals, here we explore the electronic structure and stability of OVCs and their band offsets with defect-free chalcopyrite layers in Cu- and Ag-based compounds (ABX 2 where A=Cu, Ag; B=In, Ga, Al; and X=S, Se). Using AB 3 X 5 and AB 5 X 8 stoichiometries as model OVC systems, we report on the variation of the bandgap with the A/B ratio and discuss the trends in other Cu- and Ag-based chalcopyrites beyond CuInSe 2 . We find that the valence and conduction bands are lower in energy in OVCs with respect to the parent ABX 2 chalcopyrite owing to a reduced p–d interaction between X and A atoms. We additionally perform device-level simulations to assess the implications of the results, finding that the valence band offsets of OVCs are favorable, while the conduction band offsets of chalcopyrites beyond CuInSe 2 -based absorbers may be detrimental in conventional solar cell device designs.

14 SOLAR ENERGY↗

On the Structural Transformation of Ni/BaH 2 During a N 2 -H 2 Chemical Looping Process for Ammonia Synthesis: A Joint In Situ Inelastic Neutron Scattering and First-Principles Simulation Study

The demand for decarbonizing the ammonia industry by using renewable energy has invoked increasing research interests into catalyst development for effective N 2 reduction under mild conditions. Hydride-based materials are among some of the emerging catalysts for ammonia synthesis at ambient pressure and low temperatures (< 673 K). A recent chemical looping process based on Ni/BaH 2 showed the most promise as it can realize ammonia production at a temperature as low as 373 K and under ambient pressure. However, the chemical transformation of the hydride catalyst at the molecular level remains unclear in this process. Here, we report detailed in situ neutron spectroscopy and diffraction investigations along with first-principles simulations on the structural transformation of Ni/BaH 2 during the nitridation and hydrogenation steps in the chemical looping process for ammonia synthesis. It was shown that a ball-milling process of the starting Ni/BaH 2 could significantly decrease the size of BaH 2 and increase the density of defects, thus potentially enhancing the reactivity of the hydride. The evolution from BaH 2 to barium imide (BaNH) was evidenced in the inelastic neutron scattering (INS) and neutron diffraction results during the N 2 reaction step. During the hydrogenation study, in addition to the recovery of BaH 2 , a possible intermediate species, N-deficient barium imide, was also detected. In comparing the N 2 and H 2 reaction steps, the neutron results indicate that the hydrogenation step appears more difficult than the nitridation step, confirming the facile N 2 fixation property of Ni/BaH 2 catalyst in ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗