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At least 1,153 records · Page 64

High-Temperature Gas Sensor Materials with Properties Predicted via First-Principles Calculations with Machine Learning Modeling and Experimental Corroboration

Understanding the temperature dependence of functional properties of sensing materials is vital for their applications in combustion environments. The electron-phonon coupling that derives the electronic structure change with temperatures is a key property of interest as it affects other sensing responses. Herein, we first assess the temperature dependence of band gap renormalization in sensing materials by employing Allen-Heine-Cardona (AHC) theory with density functional theory (DFT) simulations corroborated with experimental observation. As the AHC calculations are impractical for high-throughput screening of materials, we employ data-driven Gaussian process regression to predict the parameters employed in the O’Donnell empirical model from a set of physical features. To mitigate the reliability issues arising from the small size of the dataset, we apply a Bayesian technique to improve the generalizability of the data-driven models as well as to quantify the uncertainty associated with theoretical predictions. These models capture well the overall trend of the O’Donnell parameters with respect to a reduced feature set obtained by transforming the available physical features. Quantifying the associated uncertainty helps us understand the reliability of the predictions and, therefore, the variation of bandgap as a function of temperature for other novel materials. The predicted candidates from machine learning models are further validated by experiments and DFT calculations.

bandgap renormalization↗

First-principles studies of the structural, electronic, and optical properties of a novel thorium compound Rb{sub 2}Th{sub 7}Se{sub 15}

The structural, electronic, and optical properties of a recently synthesized thorium compound Rb{sub 2}Th{sub 7}Se{sub 15} have been calculated in the density functional theory framework for the first time. The calculated direct band gap was 1.471 eV (generalized gradient approximation) and 1.171 eV (local density approximation), with both results being close to the experimental result of 1.83 eV. High covalency/iconicity of the Th–Se/Rb–Se bonds was demonstrated by calculating effective Mulliken charges of all ions. The polarized calculations of the complex dielectric function are presented; dependence of the calculated index of refraction was fitted to the Sellmeyer equation in the wavelength range from 500 to 2500 nm. - Graphical abstract: Calculated band structure of Rb{sub 2}Th{sub 7}Se{sub 15}. - Highlights: • The first theoretical analysis of the Rb{sub 2}Th{sub 7}Se{sub 15} properties is reported. • Structural, electronic and optical properties of Rb{sub 2}Th{sub 7}Se{sub 15} were calculated. • An indirect character of Rb{sub 2}Th{sub 7}Se{sub 15} band gap was confirmed. • Dependence of the refractive index on the wavelength was calculated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FIRST-PRINCIPLES CALCULATIONS OF INTRINSIC DEFECTS AND Mg TRANSMUTANTS IN 3C-SiC

Silicon carbide (SiC) possesses many desirable attributes for applications in high-temperature and neutron radiation environments. These attributes include excellent dimensional and thermodynamic stability, low activation, high strength, and high thermal conductivity. Therefore, SiC based materials draw broad attention as structural materials for the first wall (FW) and blanket in fusion power plants. Under the severe high-energy neutron environment of D-T fusion systems, SiC suffers significant transmutation resulting in both gaseous and metallic transmutants. Recent calculations by Sawan, et al. [2] predict that at a fast neutron dose of ~100 dpa, there will be about 0.5 at% Mg generated in SiC through nuclear transmutation. Other transmutation products, including 0.15 at% Al, 0.2 at% Be and 2.2 at% He, also emerge. Formation and migration energies of point defects in 3C-SiC have been widely investigated using density functional theory (DFT). However, the properties of defects associated with transmutants are currently not well understood. Fundamental understanding of where the transmutation products go and how they affect microstructure evolution of SiC composites will help to predict property evolution and performance of SiC-based materials in fusion reactors.

Environmental Molecular Sciences Laboratory↗

First-principles study of superconductivity in α and β gallium

Elemental gallium can exist in several phases under ambient pressure. The stable α phase has a superconducting transition temperature, T c , of 0.9 K. By contrast, the T c of the metastable β phase is around 6 K. To understand the significant improvement in T c in the β phase, we first calculate the electronic structure, phonon dispersion, and the electron-phonon coupling of gallium in the α and β phases. Next, we solve the Eliashberg equations to obtain the superconducting gaps and the transition temperatures. Additionally, using these results, we relate the increased T c in the β phase to structural differences between the phases that affect the electronic and phonon properties. The structure motif of the α phase is Ga 2 dimers, which form strong covalent bonds leading to bonding and antibonding states that reduce the density of states at the Fermi level. The β-Ga structure consists of arrays of Ga chains that favor strong coupling between the lattice vibrations and the electronic states near the Fermi level. The increased density of states and strong coupling to the phonons for the β-Ga chains compared to the αGa 2 dimers enhance superconductivity in the β-Ga phase.

36 MATERIALS SCIENCE↗

First-Principles Study of Tritium Trapping by Point Defects in Fe-Al Aluminide Coating Phases

Density functional theory simulations have been carried out to investigate the potential for tritium trapping by metal vacancies in five different Fe-Al aluminide coating phases. It was found that tritiation of Fe and Ni vacancies is generally less favorable than the tritiation of Al vacancies. However, for the first tritiation, a trend in the defect formation energy can be obtained such that metal defects in the Fe 2 Al x family of materials (i.e., Fe 2 Al 4 , Fe 2 Al 5 , and Fe 2 Al 6 ) trap tritium species more favorably than metal vacancies in Fe 4 Al 13 and FeNiAl 5 . Further investigations using ab initio thermodynamics calculations confirmed that trend for a range of tritium partial pressure at a temperature of 700 K. Especially, it was shown that the energy difference between tritiated and non-tritiated metal vacancies is smaller and more favorable for the Fe 2 Al x family, followed by Fe 4 Al 13 , and FeNiAl 5 . While this study shows that tritium interacts differently in the various Fe-Al aluminide phases, it also suggests that tritium trapping and retention could be more efficient if metal defects are present in some Fe-Al phases.

36 MATERIALS SCIENCE↗

First-principles simulations of 2-D semiconductor devices: Mobility, I-V characteristics, and contact resistance

We report in this paper ab-initio quantum transport simulations of different types of single-layer 2-D semiconductors: transition metal and group IV dichalcogenides in the 2H or 1T phase as well as black phosphorus. The electron and hole phonon-limited mobilities of eight selected 2-D crystals are first analyzed before using these materials as n- or p-type channels of ultra-scaled single-gate transistors, computing their I-V characteristics in the presence of electron-phonon scattering, and comparing them to each other. Finally, the properties of metal-MoS 2 contacts are investigated. It is revealed that the current tends to flow at the edge of the metal layer before entering the semiconductor, thus limiting the injection efficiency.

Luisier, M.↗

Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

Two series of lanthanide complexes were chosen to analyze the trends of the magnetic properties along the series: the highly symmetric LnZn 16 (picHA) 16 series with Ln = Tb, Dy, Ho, Er, Yb and picHA=picoline hydroxamic, and the [Ln(DPA) 3 ](C 3 H 5 N 2 ) 3 · 3H 2 O series with DPA = 2,6-dipicolinic acid and Ln = Ce–Yb and the approximate threefold symmetry. The first series present a compressed coordination sphere of 8 oxygen atoms environment while in the 2nd series, the coordination sphere is formed by an elongated coordination sphere formed by 6 oxygen atoms. Crystal field parameters (CFPs) are deduced from ab initio calculations using two methods: the AILFT (Ab Initio Ligand Field Theory) which determines the parameters at the orbital level, and the ITO (Irreducible Technique Operator) decomposition which treats the problem at the many-electron level. It is shown that the CFPs are transferable from one derivative to the other, within a given series. The sign of the 2nd order parameter $B_0^2$ differs in the two series reflecting the difference of environment. It is shown that the use of strength parameter $S$ permits a easy comparison between complexes. Furthermore, in both cases, the parameters are found to decrease in magnitude along the series and this decrease is imputed to covalent effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-principles investigation of the dissociation and coupling of methane on small copper clusters: Interplay of collision dynamics and geometric and electronic effects

Small metal clusters exhibit unique size and morphology dependent catalytic activity. The search for alternate minimum energy pathways and catalysts to transform methane to more useful chemicals and carbon nanomaterials led us to investigate collision induced dissociation of methane on small Cu clusters. We report here for the first time, the free energy barriers for the collision induced activation, dissociation, and coupling of methane on small Cu clusters (Cu{sub n} where n = 2–12) using ab initio molecular dynamics and metadynamics simulations. The collision induced activation of the stretching and bending vibrations of methane significantly reduces the free energy barrier for its dissociation. Increase in the cluster size reduces the barrier for dissociation of methane due to the corresponding increase in delocalisation of electron density within the cluster, as demonstrated using the electron localisation function topology analysis. This enables higher probability of favourable alignment of the C–H stretching vibration of methane towards regions of high electron density within the cluster and makes higher number of sites available for the chemisorption of CH{sub 3} and H upon dissociation. These characteristics contribute in lowering the barrier for dissociation of methane. Distortion and reorganisation of cluster geometry due to high temperature collision dynamics disturb electron delocalisation within them and increase the barrier for dissociation. Coupling reactions of CH{sub x} (x = 1–3) species and recombination of H with CH{sub x} have free energy barriers significantly lower than complete dehydrogenation of methane to carbon. Thus, competition favours the former reactions at high hydrogen saturation on the clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-Principles Study of Lithium Cobalt Spinel Oxides: Correlating Structure and Electrochemistry

Embedding a lithiated cobalt oxide spinel (Li 2 Co 2 O 4 , or LiCoO 2 ) component or a nickel-substituted Li2Co 1-x NixO 2 analogue in structurally integrated cathodes such as xLi 2 MnO 3 .(1-x)LiM'O 2 (M' = Ni/Co/Mn) has been recently proposed as an approach to advance the performance of lithium-ion batteries. Here, we first revisit the phase stability and electrochemical performance of LiCoO 2 synthesized at different temperatures using density functional theory calculations. Consistent with previous studies, we find that the occurrence of low- and high-temperature structures (i.e., cubic lithiated spinel LT-LiCoO 2 ; or Li 2 Co 2 O 4 (Fd$\overline{3m}$) vs trigonal-layered HT-LiCoO 2 (R$\overline{3m}$), respectively) can be explained by a small difference in the free energy between these 20 30 40 50 60 70 80 26 two compounds. Additionally, the observed voltage profile of a Li/LiCoO 2 cell for both cubic and trigonal phases of LiCoO 2 , as well as the migration barrier for lithium diffusion from an octahedral (O h ) site to a tetrahedral site (T d ) in Fd$\overline{3m}$ LT-Li 1-x CoO 2 , has been calculated to help understand the complex electrochemical charge/discharge processes. A search of LiCo x M 1-x O 2 lithiated spinel (M' = Ni or Mn) structures and compositions is conducted to extend the exploration of the chemical space of Li-Co-Mn-Ni-O electrode materials. We predict a new lithiated spinel material, LiNi 0.8125 Co 0.1875 O 2 (Fd$\overline{3m}$), with a composition close to that of commercial, layered LiNi 0.8 Co 0.05 Al 0.05 O 2 , which may have the potential for exploitation in structurally integrated, layered spinel cathodes for next generation lithium-ion batteries.

25 ENERGY STORAGE↗

First-principles Prediction of X-Ray Polarization from Magnetic Reconnection in High-frequency BL Lacertae Objects

Relativistic magnetic reconnection is a potential particle acceleration mechanism for high-frequency BL Lac objects (HBLs). The Imaging X-ray Polarimetry Explorer (IXPE) scheduled to launch in 2021 has the capability to probe the evolution of magnetic field in HBLs, examining the magnetic reconnection scenario for the HBL flares. In this paper, we make the first attempt to self-consistently predict HBL X-ray polarization signatures arising from relativistic magnetic reconnection via combined particle-in-cell and polarized radiation transfer simulations. Here, we find that although the intrinsic optical and X-ray polarization degrees are similar on average, the X-ray polarization is much more variable in both the polarization degree and angle (PD and PA). Given the sensitivity of the IXPE, it may obtain one to a few polarization data points for one flaring event of nearby bright HBLs Mrk 421 and 501. However, it may not fully resolve the highly variable X-ray polarization. Due to temporal depolarization, where the integration of photons with variable polarization states over a finite period of time can lower the detected PD, the measured X-ray PD can be considerably lower than the optical counterpart or even undetectable. The lower X-ray PD than the optical thus can be a characteristic signature of relativistic magnetic reconnection. For very bright flares where the X-ray polarization is well resolved, relativistic magnetic reconnection predicts smooth X-ray PA swings, which originate from large plasmoid mergers in the reconnection region.

79 ASTRONOMY AND ASTROPHYSICS↗

Thermal conductivity of InN with point defects from first principles

We present ab initio calculations of thermal conductivity of InN with vacancies and substitutional defects using a full solution of the Peierls-Boltzmann transport equation. Our parameter-free calculations are in good agreement with experimental measurements demonstrating the predictive power of this approach. Phonon-defect scattering rates are computed from a Green's function methodology that is nonperturbative and includes interatomic force constant variance induced near the defects. Restricting calculations to first-order perturbation approaches can overestimate optic phonon scattering rates by nearly three orders of magnitude. On the other hand, neglecting the force variance weakens the scattering rates by about an order of magnitude, mostly in the low-frequency region below 2 THz. Here, this work elucidates important properties of phonon-defect scattering in thermal transport and demonstrates the predictive power of the coupling of Peierls-Boltzmann transport, Green's function methods, and density functional theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural, electronic, mechanical, and dynamical properties of graphene oxides: A first principles study

We report the results of a theoretical study on the structural, electronic, mechanical, and vibrational properties of some graphene oxide models (GDO, a-GMO, z-GMO, ep-GMO and mix-GMO) at ambient pressure. The calculations are based on the ab-initio plane-wave pseudo potential density functional theory, within the generalized gradient approximations for the exchange and correlation functional. The calculated values of lattice parameters, bulk modulus, and its first order pressure derivative are in good agreement with other reports. A linear response approach to the density functional theory is used to derive the phonon frequencies. We discuss the contribution of the phonons in the dynamical stability of graphene oxides and detailed analysis of zone centre phonon modes in all the above mentioned models. Our study demonstrates a wide range of energy gap available in the considered models of graphene oxide and hence the possibility of their use in nanodevices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI 3 and Their Role in Stabilization

The stability of halide perovskites has been a long-standing issue for their real-world application. Approaches to improve stability include nanostructuring, dimensionality reduction, and strain engineering, where surfaces play an important role in the formation of a stable structure. To understand the mechanism we compute the lattice dynamics of the surface of CsPbI 3 using density functional theory. We demonstrate, for the first time, that CsPbI 3 crystals exhibit surface phonons that are localized on the outermost layers of the slabs, and we perform a complete symmetry characterization including an identification of the Raman/IR active modes. These surface phonons are present in the optically active cubic phase but are absent in the optically inactive "yellow" phase. Furthermore, we show that the surface suppresses bulk instabilities by hardening soft modes of the bulk cubic phase, resulting in phase stabilization and quenching of dynamical disorder. Finally, this study is fundamental for understanding the structural behavior of halide perovskite materials with high surface area-to-volume ratios, and for guiding stabilization strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Viscosity in water from first-principles and deep-neural-network simulations

Abstract We report on an extensive study of the viscosity of liquid water at near-ambient conditions, performed within the Green-Kubo theory of linear response and equilibrium ab initio molecular dynamics (AIMD), based on density-functional theory (DFT). In order to cope with the long simulation times necessary to achieve an acceptable statistical accuracy, our ab initio approach is enhanced with deep-neural-network potentials (NNP). This approach is first validated against AIMD results, obtained by using the Perdew–Burke–Ernzerhof (PBE) exchange-correlation functional and paying careful attention to crucial, yet often overlooked, aspects of the statistical data analysis. Then, we train a second NNP to a dataset generated from the Strongly Constrained and Appropriately Normed (SCAN) functional. Once the error resulting from the imperfect prediction of the melting line is offset by referring the simulated temperature to the theoretical melting one, our SCAN predictions of the shear viscosity of water are in very good agreement with experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First principles study on electronic structure and elastic properties of LaCd and LaHg

Full -potential linearized augmented plane wave method (FP- LAPW) has been used for the comparative study of electronic structure and elastic properties of CsCl-type LaCd and LaHg intermetallic compounds using generalized gradient approximation (GGA). The density of states at the Fermi Level, N (E{sub F}), is found to be 0.06 and 3.03 states/eV for LaCd and LaHg respectively. We report elastic constants for these compounds for the first time. The ductility/brittleness of these compounds has been analyzed using Pugh rule and Cauchy’s pressure.

36 MATERIALS SCIENCE↗

First-principles study of the structures and redox mechanisms of Ni-rich lithium nickel manganese cobalt oxides

To reduce the cobalt (Co) content in lithium-ion batteries, Ni-rich (high-Ni) lithium nickel manganese cobalt oxides (NMC) are pursued as one of the next-generation cathode materials. However, there is still debate on the crystal and electronic structures of the baseline, LiNiO 2 . Density Functional Theory (DFT) calculations were performed to provide a theoretical understanding of Ni-rich NMC. First, it was found that the commonly used $R\bar{3}m$ structure for LiNiO 2 is metallic, contrary to the experimentally reported mix-conducting behavior. Among the four different space groups, $R\bar{3}m$, C2/m, P2 1 /c, and P2/c, P2/c with charge disproportionation of Ni 2+ and Ni 4+ is the most energetically stable and semiconducting structure of LiNiO 2 . Therefore, the atomic structures of representative Ni-rich NMC were built by partially replacing Ni with Co or Mn in the P2/c LiNiO 2 to form Li x Ni y Mn z Co 1-y-z O 2 . In the fully lithiated (x=1.0) high Ni content NMC (y>0.5), the oxidation state of all Mn ions becomes 4+, while Co ions still maintain 3+, and part of the Ni ions become 3+ to compensate for the charge. Upon delithiation, the local environment shows more variation of the charge states on the transition metal (TM) ions. The average oxidation on each TM follows a sequence of losing electrons that starts from Ni 2+ to Ni 3+ , then oxidizing Ni 3+ and Co 3+ , while Mn 4+ remains electrochemically inactive till x=0. Finally, a general relationship for the oxidation state change in each TM as a function of x is derived and shows agreement with both modeling and experimental data.

25 ENERGY STORAGE↗

A first principles approach to the electronic properties of liquid and supercritical CO{sub 2}

The electronic absorption spectra of liquid and supercritical CO{sub 2} (scCO{sub 2}) are investigated by coupling a many-body energy decomposition scheme to configurations generated by Born-Oppenheimer molecular dynamics. A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies were calculated with time dependent density functional theory. A red-shift of ∼ 0.2 eV relative to the gas-phase monomer is observed for the first electronic absorption maximum in liquid and scCO{sub 2}. The origin of this shift, which is not very dependent on deviations from the linearity of the CO{sub 2} molecule, is mainly related to polarization effects. However, the geometry changes of the CO{sub 2} monomer induced by thermal effects and intermolecular interactions in condensed phase lead to the appearance of an average monomeric electric dipole moment 〈μ〉 = 0.26 ± 0.04 D that is practically the same at liquid and supercritical conditions. The predicted average quadrupole moment for both liquid and scCO{sub 2} is 〈Θ〉 = − 5.5 D Å, which is increased by ∼ −0.9 D Å relative to its gas-phase value. The importance of investigating the electronic properties for a better understanding of the role played by CO{sub 2} in supercritical solvation is stressed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-radiative carrier recombination enhanced by two-level process: A first-principles study

In this study, non-radiative recombination plays an important role in the performance of optoelectronic semiconductor devices such as solar cells and light-emitting diodes. Most textbook examples assume that the recombination process occurs through a single defect level, where one electron and one hole are captured and recombined. Based on this simple picture, conventional wisdom is that only defect levels near the center of the bandgap can be effective recombination centers. Here, we present a new two-level recombination mechanism: first, one type of carrier is captured through a defect level forming a metastable state; then the local defect configuration rapidly changes to a stable state, where the other type of carrier is captured and recombined through another defect level. This novel mechanism is applied to the recombination center Te 2+ cd in CdTe. We show that this two-level process can significantly increase the recombination rate (by three orders of magnitude) in agreement with experiments. We expect that this two-level recombination process can exist in a wide range of semiconductors, so its effect should be carefully examined in characterizing optoelectronic materials.

14 SOLAR ENERGY↗