Average Atom Research Articles

Extensive Theoretical Study of the Thermochemical Properties of Unsaturated Hydrocarbons and Allylic and Super-Allylic Radicals: The Development and Optimization of Group Additivity Values.

In this study, the thermochemistry of C2-C7 unsaturated hydrocarbons (22 alkene and 6 diene molecules) and 16 allylic and 5 super-allylic radicals is determined using high-accuracy quantum chemistry calculations. In addition, the group additivity values (GAVs) of a total of 19 relevant groups are systematically optimized on the basis of the calculated thermochemistry of species clusters. The M06-2X method using the 6-311++G(d,p) basis set is used for the geometry optimizations, vibrational frequency calculations, and internal rotation scans for lower-frequency modes. The composite compound methods, CBS-APNO, G3, and G4, are utilized to derive the average atomization formation enthalpies. The entropy and temperature-dependent heat capacity values of all species are calculated using statistical thermodynamics in MultiWell. These results are in good agreement with literature data. A GAVs optimization is performed on the basis of a statistical analysis: a Bland-Altman plot, which is employed to visualize the agreement between the results from the quantum chemical calculations and the GA method. It is found that the 298 K entropies of the CD/C2, C/CD2/H2, C/C/CD2/H, and C/CD3/H groups disagree by more than 5 cal K-1 mol-1 compared to existing values, while the values for the ALLYLS and ALLYLT radical groups also differ by ∼2.4 and 4.1 cal K-1 mol-1, respectively. The 298 K formation enthalpies of the C/CD2/H2, C/C/CD2/H, C/CD3/H, and ALLYLT groups are modified by more than 1 kcal mol-1, compared to existing values. The updated GAVs can be used with increased confidence to estimate the thermochemical properties of combustion-relevant unsaturated hydrocarbon molecules and their radicals which are critical for the development of accurate chemical kinetic models describing the pyrolysis and oxidation of hydrocarbon and oxygenated hydrocarbon fuels.

Hugoniot equation of state of Si-doped glow discharge polymer and scaling to other plastic ablators

Pressure, density, and temperature were measured along the principal Hugoniot of the Si-doped Glow Discharge Polymer used in Inertial Confinement Fusion (ICF) capsules up to 5 Mbar, covering conditions beyond the first shock in a full-scale Inertial Confinement Fusion (ICF) capsule. The experiments were performed using the GEKKOXII laser at the Institute of Laser Engineering at Osaka University in Japan. Results are in good agreement with predictions obtained from ab initio Hugoniot calculations, but softer than the quotidian equation of state average atom model. Ab initio calculations show that dissociation of carbon bonds need to be taken into account in order to explain Hugoniot compressibility.

Calculation of Temporal Plasmas of XFEL Experiments with a Relativistic Collisional Radiative Average Atom Code

Calculation of Temporal Plasmas of XFEL Experiments with a Relativistic Collisional Radiative Average Atom Code

Two-photon exchange interaction from the Dicke Hamiltonian under parametric modulation

We consider the nonstationary circuit QED architecture in which a single-mode cavity interacts with N>1 identical qubits, and some system parameters undergo a weak external perturbation. It is shown that in the dispersive regime one can engineer the two-photon exchange interaction by adjusting the frequency of harmonic modulation to (approximately) $2|\Delta _{-}|$, where $\Delta _{-}$ is the average atom--field detuning. Closed analytic description is derived for the weak atom-field coupling regime, and numeric simulations indicate that the phenomenon can be observed in the present setups.

Estimating the densities of benzene-derived explosives using atomic volumes.

The application of average atomic volumes to predict the crystal densities of benzene-derived energetic compounds of general formula C a H b N c O d is presented, along with the reliability of this method. The densities of 119 neutral nitrobenzenes, energetic salts, and cocrystals with diverse compositions were estimated and compared with experimental data. Of the 74 nitrobenzenes for which direct comparisons could be made, the % error in the estimated density was within 0-3% for 54 compounds, 3-5% for 12 compounds, and 5-8% for the remaining 8 compounds. Among 45 energetic salts and cocrystals, the % error in the estimated density was within 0-3% for 25 compounds, 3-5% for 13 compounds, and 5-7.4% for 7 compounds. The absolute error surpassed 0.05g/cm3 for 27 of the 119 compounds (22%). The largest errors occurred for compounds containing fused rings and for compounds with three -NH2 or -OH groups. Overall, the present approach for estimating the densities of benzene-derived explosives with different functional groups was found to be reliable. Graphical abstract Application and reliability of average atom volume in the crystal density prediction of energetic compounds containing benzene ring.

Influence of shell effects on thermodynamic properties of matter at high pressures

We analyze the influence of shell effects on thermodynamic properties of matter at high pressures. Spherically symmetric average atom models show significant contribution of electronic transitions to cold pressure which is not confirmed by more accurate density functional theory models. In particular, the s–d transition in aluminum and potassium does not reveal itself on the shock Hugoniots. Oscillations on shock Hugoniots at very high pressures predicted earlier by many authors should be confirmed by precise first-principle calculations.

Dynamics of ultrasonic atomization of droplets

We investigate the atomization behavior of a droplet subjected to ultrasonic substrate vibration experimentally. High-speed imaging is employed to quantify the average atomization lifetime of the droplet as a function of initial droplet size and different fluid properties. Atomization rate increases with the initial droplet size and is also found to be very sensitive to changes in viscosity, while not so sensitive to surface tension changes. A theoretical model based on capillary wave breakup mechanism is developed, predicting these trends accurately. Our results underscore the role of capillary wave generation at the liquid-vapor interface via Faraday excitation in ultrasonic atomization. Though the capillary wavelength follows the inviscid scaling law, the wave breakup is shown to be controlled by a viscous-inertia balance.

Unconventional thermal transport enhancement with large atom mass: a comparative study of 2D transition dichalcogenides

2D layered transition dichalcogenides have attracted tremendous attention for their excellent properties and multifarious applications. In particular, NbSe2 and TaSe2 are the canonical systems to study superconductivity and charge density waves. Here, we perform a comparative study of the thermal transport properties of 2D NbSe2 and TaSe2 for both 1T and 2H phases based on first-principles calculations. Usually, the lattice thermal conductivity () is smaller with larger average atom mass. However, it is contrary for the comparison between TaSe2 and NbSe2, despite the heavier Ta than Nb. The abnormally larger of TaSe2 originates from the weakened phonon–phonon scattering due to the combination of large phonon bandgap and bunching of the acoustic phonon branches, which is caused by the larger mass difference. On one hand, the large bandgap hinders the acoustic–optical phonon scattering. On the other hand, the bunching of the acoustic phonon branches hampers Umklapp process by weakening the high frequency acoustic–acoustic phonon scattering. The special characteristics of phonon transport are further conformed by mode level analysis and scattering channels of phonon–phonon scattering. Moreover, lower κL of 1T phase for both Nb and Ta selenides compared to 2H phase are also reported, which stems from the stronger anharmonicity.

Image fusion of Secondary Ion Mass Spectrometry and Energy-dispersive X-Ray Spectroscopy data for the characterization of uranium-molybdenum fuel foils

Uranium-molybdenum (U-Mo) monolithic fuels represent one option for converting civilian research and test reactors operating with high enriched uranium (HEU) to low enriched uranium (LEU), effectively reducing the threat of nuclear proliferation world-wide. However, processes associated with fabrication of U-Mo monolithic fuels result in regions of elemental heterogeneity, observed as bands traversing the cross-section of representative samples. Isotopic variations (e.g., 235U and 238U) could also be introduced because of associated processing steps, particularly since HEU feedstock is melted with natural or depleted uranium diluent to produce LEU. This study demonstrates the utility of correlative analysis of Energy-Dispersive X-ray Spectroscopy (EDS) and Secondary Ion Mass Spectrometry (SIMS) with their image data streams using image fusion, resulting in a comprehensive microanalytical characterization toolbox. Elemental and isotopic measurements were made on a sample from the Advanced Test Reactor (ATR) Full-sized plate In-center flux trap Position (AFIP)-7 experiment and compared to previous optical and electron microscopy results. The image fusion results are characteristic of SIMS isotopic maps, but with the spatial resolution of EDS images and, therefore, can be used to increase the effective spatial resolution of the SIMS imaging results to better understand homogeneity or heterogeneity that persists because of processing selections. Visual inspection using the image fusion methodology indicated slight variations in the 235U/238U ratio and quantitative analysis using the image intensities across several FoVs revealed an average 235U atom percent value of 17.9 ± 2.4%, which was indicative of a non-uniform U isotopic distribution in the area sampled. Further development of this capability is useful for understanding the connections between the properties of LEU fuel alternatives and the ability to predict performance under irradiation.

Transport properties of warm and hot dense iron from orbital free and corrected Yukawa potential molecular dynamics

The equation of states, diffusions, and viscosities of strongly coupled Fe at 80 and 240 eV with densities from 1.6 to 40 g/cm3 are studied by orbital-free molecular dynamics, classical molecular dynamics with a corrected Yukawa potential and compared with the results from average atom model. A new local pseudopotential is generated for orbital free calculations. For low densities, the Yukawa model captures the correct ionic interaction behavior around the first peak of the radial distribution function (RDF), thus it gives correct RDFs and transport coefficients. For higher densities, the scaled transformation of the Yukawa potential or adding a short range repulsion part to the Yukawa potential can give correct RDFs and transport coefficients. The corrected potentials are further validated by the force matching method.

Electronic and optical properties of warm dense lithium: strong coupling effects

The optical properties of atoms in a hot and dense environment are of critical importance and a great challenge. In a warm dense matter, strong coupling effects between ions induce new physics which is difficult to be included in statistical isolated atom models such as the average atom model or the detailed level accounting model. Here we study the optical properties of warm dense Li from ab initio molecular dynamics with Kubo–Greenwood relations. We compare the absorption coefficients with those from detailed level accounting methods, which can show a significant difference. The analyses of ionic structures and charge density distribution show that the strongly coupled ions induce local ordered structures and redistributions of the electrons away from the homogeneous electron gases. Also, we study the electronic structures of warm dense Li within the same theoretical framework, and we discover how the local environment of different atoms affects the density of states of the system, which will directly alter the optical properties of warm dense matter.

Tartarus: A relativistic Green’s function quantum average atom code

A relativistic Green’s Function quantum average atom model is implemented in the Tartarus code for the calculation of equation of state data in dense plasmas. We first present the relativistic extension of the quantum Green’s Function average atom model described by Starrett [1]. The Green’s Function approach addresses the numerical challenges arising from resonances in the continuum density of states without the need for resonance tracking algorithms or adaptive meshes, though there are still numerical challenges inherent to this algorithm. We discuss how these challenges are addressed in the Tartarus algorithm. The outputs of the calculation are shown in comparison to PIMC/DFT-MD simulations of the Principal Shock Hugoniot in Silicon. We also present the calculation of the Hugoniot for Silver coming from both the relativistic and nonrelativistic modes of the Tartarus code.

Quantification of evaporation induced error in atom probe tomography using molecular dynamics simulation

Non-equilibrium molecular dynamics was used to simulate the dynamics of atoms at the atom probe surface and five objective functions were used to quantify errors. The results suggested that before ionization, thermal vibration and collision caused the atoms to displace up to 1Å and 25Å respectively. The average atom displacements were found to vary between 0.2 and 0.5Å. About 9 to 17% of the atoms were affected by collision. Due to the effects of collision and ion-ion repulsion, the back-calculated positions were on average 0.3–0.5Å different from the pre-ionized positions of the atoms when the number of ions generated per pulse was minimal. This difference could increase up to 8–10Å when 1.5ion/nm2 were evaporated per pulse. On the basis of the results, surface ion density was considered an important factor that needed to be controlled to minimize error in the evaporation process.

Radiative properties of matter based on quantum statistical method

We present the preliminary results of our code OPAQS (opacity calculation using quantum statistical model) that is based on the self consistent Hartree–Fock–Slater model for the average atom. The code is capable of performing robust calculations of average charge state, frequency-dependent and mean opacities. The accuracy of the atomic model is verified by comparing the calculations of average charge state with various published results. The monochromatic opacities for iron computed at different sets of temperatures and densities are compared with LEDCOP. The Rosseland and Planck opacities for iron and aluminum are validated with some state-of-the-art codes. The results are in good agreement with the published data.

Flat borophene films as anode materials for Mg, Na or Li-ion batteries with ultra high capacities: A first-principles study

Most recent exciting experimental advances introduced buckled and flat borophene nanomembranes as new members to the advancing family of two-dimensional (2D) materials. Borophene, is the boron atom analogue of graphene with interesting properties suitable for a wide variety of applications. In this investigation, we conducted extensive first-principles density functional theory simulations to explore the application of four different flat borophene films as anode materials for Al, Mg, Na or Li-ion batteries. In our modelling, first the strongest binding sites were predicted and next we gradually increased the adatoms coverage until the maximum capacity was reached. Bader charge analysis was employed to evaluate the charge transfer between the adatoms and the borophene films. Nudged elastic band method was also utilized to probe the ions diffusions. We calculated the average atom adsorption energies and open-circuit voltage profiles as a function of adatoms coverage. Our findings propose the flat borophene films as electrically conductive and thermally stable anode materials with ultra high capacities of 2480mAh/g, 1640mAh/g and 2040mAh/g for Mg, Na or Li-ion batteries, respectively, which distinctly outperform not only the buckled borophene but also all other 2D materials. Our study may provide useful viewpoint with respect to the possible application of flat borophene films for the design of high capacity and light weight advanced rechargeable ion batteries.

Comment on, “On the influence of the electron dose-rate on the HRTEM image contrast”, by Juri Barthel, Markus Lentzen, Andreas Thust, ULTRAM12246 (2016), http://dx.doi.org/10.1016/j.ultramic.2016.11.016

• Typical electron dose rates that are used to capture single high resolution images induce atom (column) displacements that greatly exceed the average atom displacements calculated from Debye–Waller factors at room temperature. • The Born–Oppenheimer breaks down during the typical acquisition of high resolution images with beam current densities that greatly exceed 1000 e/Å 2 s. • A control of electron beam-sample interactions mandates reducing beam current densities down to single electrons/Å 2 s.

Ab initio research of energy loss for energetic protons in solid-density Be

Ab initio research of energy loss for energetic protons in solid-density Be is made based on the average atom model. Our results are found in good agreement with the recent experiment for both warm and cool matter. Our results are compared with the local density approximation model and the reason for their difference is also explored. The energy loss at smaller projectile energies is predicted by our model and local density approximation, which helps probe the higher reliability of the proving model and judge the existence of the non-Fermi-Dirac velocity distribution for free electrons exists in dense plasmas in future.

Free-free opacity in dense plasmas with an average atom model

A model for the free-free opacity of dense plasmas is presented. The model uses a previously developed average atom model, together with the Kubo-Greenwood model for optical conductivity. This, in turn, is used to calculate the opacity with the Kramers-Kronig dispersion relations. Comparisons to other methods for dense deuterium results in excellent agreement with DFT-MD simulations, and reasonable agreement with a simple Yukawa screening model corrected to satisfy the conductivity sum rule. Comparisons against the very recent experiments of Kettle et al. for dense aluminum also reveal very good agreement, in contrast to existing models. Weaknesses in the model are also highlighted.

Microstructure and strain-stress analysis of the dynamic strain aging in inconel 625 at high temperature

Serrated flow is a result of unstable plastic flow, which occurs during tensile and compression tests on some dilute alloys. This phenomenon is referred as the Portevin Le-Chatelier effect (PLC effect). The aim of this research was to investigate and analyze this phenomenon in Inconel 625 solution strengthened superalloy. The tested material was subjected to tensile tests carried out within the temperature range 200-700 °C, with three different strain rates: 0.002 1/s, 0.01/s, and 0.05 1/s and additional compression tests with high deformation speeds of 0.1, 1, and 10 1/s. The tensile strain curves were analyzed in terms of intensity and the observed patterns of serrations Using a modified stress drop method proposed by the authors, the activation energy was calculated with the assumption that the stress drops’ distribution is a direct representation of an average solute atom’s interaction with dislocations. Subsequently, two models, the standard vacancy diffusion Bilby-Cottrell model and the realistic cross-core diffusion mechanism proposed by Zhang and Curtin, were compared. The results obtained show that the second one agrees with the experimental data. Additional microstructure analysis was performed to identify microstructure elements that may be responsible for the PLC effect. Based on the results, the relationship between the intensity of the phenomenon and the conditions of the tests were determined.

Molecular field origin for magnetic ordering of magnetic materials

In 1907, Weiss proposed that there is a molecular field to explain the magnetic ordering of magnetic materials. However, it has not been clarified where the molecular field comes from so far. In recent decades, the magnetic ordering of metals and alloys were explained by using the direct exchange interaction of between electrons on neighboring atoms, while magnetic ordering of oxides were explained by using the super exchange interaction and double exchange interaction models. The intrinsic relation between those exchange interactions has not been well explained. This resulted in the fact that there are many puzzles for magnetic ordering of the magnetic materials. For example, what role the Cr cations play in spinel ferrite CrFe2O4; why the calculated molecular magnetic moment (3.85B) for La0.85Sr0.15MnO3 by using double exchange interaction model is lower than its experimental value (4.20B); whether there is a relation between the average atom magnetic moment and their electrical resistivity for each of Fe, Co and Ni metals. These several puzzles have been explained recently by our group through using an O 2p itinerant electron model for magnetic oxides and a new itinerant electron model for magnetic metals. In this paper, a model for the molecular field origin is proposed. There are three states for the electrons rotating with high speed at the outer orbits of two adjacent ions of magnetic oxides or metals and alloys. 1) There is a probability with which form the electron pairs with opposite spin directions and a certain life time, named Weiss electron pairs (WEP); the static magnetic attraction energy between two electrons of WEP is the elementary origin of Weiss molecular field. 2) There is a probability with which two electrons with the same spin direction exchange mutually. 3) If there are two electrons at the outer orbit of an ion, then for its adjacent ion whose orbit has only one electron, the excess electron will itinerates between the ions. Furthermore, the energy equation of WEP, equilibrium distance, re0, and maximum distance, rem, between electrons of WEP are derived. The probability with which WEP forms in each of several perovskite manganites is investigated. For perovskite manganites La0.8Ca0.2MnO3, La0.75Ca0.25MnO3, La0.70Sr0.30MnO3, the crystal cell constants increase linearly with temperature when the temperature is much lower than the Curie temperature, TC, while they show a rapid increase nonlinearly near TC. We then calculate the difference in MnO bond length at TC between the linear and the nonlinear variation, △dobs. Obviously, when the distance between the two electrons of WEP, re, is larger than the rem, WEP and the magnetic ordering energy both disappear. Assuming △dobs=rem-re0, the probabilities with which WEP appears in La0.8Ca0.2MnO3, La0.75Ca.25MnO3, La0.70Sr0.30MnO3, are calculated to be 0.07%, 0.31% and 3.13%, respectively. These results indicate that the WEP model for the magnetic ordering energy is qualitatively reasonable.