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At least 19 records

Ab initio study of the alkali and alkaline-earth monohydroxides

A systematic study of the structures and dissociation energies of all the alkali and alkaline-earth monohydroxides is conducted. A theoretical model for determining accurate dissociation energies of ionic molecules is discussed. The obtained theoretical structures and dissociation energies of the alkali and alkaline-earth monohydroxides, respectively, are compared with experimental data. It is found that the theoretical studies of the bending potentials of BeOH, MgOH, and CaOH reveal the different admixture of covalent character in these systems. The BeOH molecule with the largest degree of covalent character is found to be bent (theta equals 147 deg). The MgOH is also linear. The theoretical dissociation energies for the alkali and akaline-earth hydroxides are thought to be accurate to 0.1 eV.

Bauschlicher, C. W., Jr.↗

Superconducting critical fields of alkali and alkaline-earth intercalates of MoS2

Results are reported for measurements of the critical-field anisotropy and temperature dependence of group-VIB semiconductor MoS2 intercalated with the alkali and alkaline-earth metals Na, K, Rb, Cs, and Sr. The temperature dependences are compared with present theories on the relation between critical field and transition temperature in the clean and dirty limits over the reduced-temperature range from 1 to 0.1. The critical-field anisotropy data are compared with predictions based on coupled-layers and thin-film ('independent-layers') models. It is found that the critical-field boundaries are steep in all cases, that the fields are greater than theoretical predictions at low temperatures, and that an unusual positive curvature in the temperature dependence appears which may be related to the high anisotropy of the layer structure. The results show that materials with the largest ionic intercalate atom diameters and hexagonal structures (K, Rb, and Cs compounds) have the highest critical temperatures, critical fields, and critical-boundary slopes; the critical fields of these materials are observed to exceed the paramagnetic limiting fields.

Woollam, J. A.↗

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

Langhoff, S. R.↗

Theoretical study of the dipole moments of selected alkaline-earth halides

Ab initio calculations at the self-consistent-field (SCF), singles-plus-doubles configuration-interaction (SDCI), and coupled-pair functional (CPF) level, are reported for the dipole moments and dipole derivatives of the X2Sigma(+) ground states of BeF, BeCl, MgF, MgCl, CaF, CaCl, and SrF. For comparison, analogous calculations are performed for the X1Sigma(+) state of KCl. The CPF results are found to be in remarkably better agreement with experiment than are the SCF and SDCI results. Apparently higher excitations are required to properly describe the radial extent along the bond axis of the remaining valence electron on the alkaline-earth metal.

Langhoff, S. R.↗

EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

Fryburg, G. C.↗

A Transferable Force Field for Predicting Adsorption and Diffusion of Water in Cationic Zeolites with Coupled Cluster Accuracy

We present a transferable force field for water in proton-exchanged, alkali (Li, Na, K, Rb, and Cs) metal-exchanged, and alkaline-earth (Mg, Ca, Sr, and Ba) metal-exchanged zeolites. The fitting methodology is based on adsorbate–adsorbent interaction energies obtained from periodic density functional theory calculations and corrected using the coupled-cluster method applied to small model clusters. To ensure an accurate prediction of both adsorption and diffusion properties of water, sets of configurations that sample both adsorption sites and intracrystalline hopping transition states were used in the fitting. The quality of the force field is assessed for a wide range of zeolites with different topologies and chemical compositions, demonstrating good agreement between theoretical predictions and experimental measurements of water adsorption and diffusion.

Adsorption↗

Structure–property relations of binary ferrite melts

Molten ferrite systems are used in the smelting and refining processes in steelmaking, to reduce the loss of metals in slags and to accelerate reaction rates. Here, high-energy x-ray diffraction experiments have been performed on aerodynamically levitated molten spheres of 43BaO–57FeO X and 43SrO–57FeO X at 1873 K using laser beam heating. The composition was varied within the range of x = 1–1.5 by changing the oxygen partial pressure of the levitation gas. The corresponding x-ray pair distribution functions have been interpreted using empirical potential structure refinement (EPSR) modeling. In oxygen-rich melts (x = 1.5), our EPSR models indicate very similar structures for the different alkaline-earth liquids, with both the Ba–O and Sr–O coordination numbers to be ∼8.4 and the total Fe–O coordination numbers ∼5.7. However, our models show that in reducing environments, the Fe 3+ and Fe 2+ ions exhibit very different behaviors in the Ba- and Sr-ferrite liquids. In the Ba-ferrite melt, the Fe 3+ –O coordination number decreases from 5.7 (at x = 1.5) to 5.2 (at x = 1.07), whereas Fe 2+ –O remains constant at ∼5.0 across the same compositional range. In the Sr melts, both the Fe 2+ –O and Fe 3+ –O coordination numbers rise from ∼5.7 (at x = 1.5) to 6.3 (at x = 1.07). All models show the structures to be heterogeneous with intertwined nanometer sized clusters or channels of Ba/Sr–O and Fe–O polyhedra that grow as oxygen content is reduced. Changes in the viscosity and electrical properties are interpreted in terms of the number of bridging and non-bridging oxygens associated with FeO 4 tetrahedra and concentration of charge carriers, respectively.

Benmore, Chris J. [Argonne National Laboratory (AN↗

Epitaxial PbGeSe thin films and their photoluminescence in the mid-wave infrared

PbSe is a narrow bandgap IV–VI compound semiconductor with application in mid-wave infrared optoelectronics, thermoelectrics, and quantum devices. Alkaline-earth or rare-earth elements such as Sr and Eu can substitute Pb to widen the bandgap of PbSe in heterostructure devices, but they come with challenges such as deteriorating optical and electronic properties, even in dilute concentrations due to their dissimilar atomic nature. We substitute Pb instead with column IV Ge and assess the potential of rocksalt phase PbGeSe as a wider bandgap semiconductor in thin films grown by molecular beam epitaxy on GaAs substrates. Low sticking of GeSe adatoms requires synthesis temperatures below 260 °C to incorporate Ge, but this yields poor structural and compositional uniformity as determined by x-ray diffraction. Consequently, as-grown films in the range Pb0.94Ge0.06Se–Pb0.83Ge0.17Se (6%–17% Ge) show much less bandgap widening in photoluminescence than prior work on bulk crystals using absorption. We observe that post-growth rapid thermal annealing at temperatures of 375–450 °C improves the crystal quality and recovers bandgap widening. Rapid interdiffusion of Ge during annealing, however, remains a challenge in harnessing such PbGeSe materials for compositionally sharp heterostructures. Annealed 17% Ge films emit light at 3–3.1 μm with a minimal shift in wavelength vs temperature. These samples are wider in bandgap than PbSe films by 55 meV at room temperature, and the widening increases to 160 meV at 80 K, thanks to sharply different dependence of bandgap on temperature in PbSe vs PbGeSe.

Xiao, Kelly (ORCID:0000000321000838)↗

Unit-density SU(3) Fermi-Hubbard model with spin-flavor imbalance

The advent of ultracold alkaline-earth atoms in optical lattices has established a platform for investigating correlated quantum matter with SU⁡(𝑁) symmetry, offering highly tunable model parameters that allow experiments to access phenomena that are unavailable in conventional materials. Understanding the ground-state physics of SU⁡(𝑁) Fermi-Hubbard models away from the Heisenberg limit and from the spin-flavor balanced setting is important, as examining the flavor imbalance reveals new physics in Fermi-Hubbard models and shows how SU⁡(𝑁) phases react to practical experimental imperfections in optical lattices. Here, in this study, mean-field phase diagrams are presented for the unit-density SU(3) Fermi-Hubbard model at two sets of flavor densities, ($\frac{1}{3}$ − 𝛿, $\frac{1}{3}$ + 𝛿, $\frac{1}{3}$) and ($\frac{1}{4}$ − 𝛿, $\frac{1}{4}$ +𝛿, $\frac{1}{2}$), with the flavor imbalance introduced as 𝛿. Novel phases are identified at moderate interaction strengths for both densities, and their robustness is investigated in the presence of flavor imbalance. Furthermore, we provide microscopic explanations of the phases found and their stability. Analysis of thermal ensembles of random mean-field solutions indicate that, at temperatures accessible in state-of-the-art cold atom experiments, some spin orders are hard for conventional scattering or local observable measurements to detect, but can be more accessible with quantum gas microscopy in optical lattice experiments. This work also shows that nesting and Mottness, intertwined in the usual SU(2) Hubbard model in stark contrast to generic materials, can be tuned in the SU(3) model and play distinct roles. The resulting phase diagrams not only deepen our understanding of SU⁡(𝑁) Fermi-Hubbard models but also inform future experimental search for new phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Superconductivity in a topological lattice model with strong repulsion

The highly tunable nature of synthetic quantum materials-both in the solid-state and cold atom contexts-invites examining which microscopic ingredients aid in the realization of correlated phases of matter such as superconductors. Recent experimental advances in moiré materials suggest that unifying the features of the Fermi-Hubbard model and quantum Hall systems creates a fertile ground for the emergence of such phases. Here, we introduce the "double Hofstadter"model, a minimal 2D lattice model that incorporates exactly these features: Time-reversal symmetry, band topology, and strong repulsive interactions. By using infinite cylinder density matrix renormalization group methods (cylinder iDMRG), we investigate the ground state phase diagram of this model. We find that it hosts an interaction-induced quantum spin Hall insulator and demonstrate that weakly hole-doping this state gives rise to a superconductor at a finite circumference, with indications that this behavior persists on larger cylinders. Further, at the aforementioned circumference, the superconducting phase is surprisingly robust to perturbations including additional repulsive interactions in the pairing channel. By developing a technique to probe the superconducting gap function in iDMRG, we phenomenologically characterize the superconductor. Namely, we demonstrate that it is formed from the weak pairing of holes atop the quantum spin Hall insulator. Furthermore, we determine the pairing symmetry of the superconductor, finding it to be p-wave-reminiscent of the unconventional superconductivity reported in experiments on twisted bilayer graphene (TBG). Motivated by this, we elucidate structural similarities and differences between our model and those of TBG in its chiral limit. Finally, to provide a more direct experimental realization, we detail an implementation of our Hamiltonian in a system of cold fermionic alkaline-earth atoms in an optical lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Kinetics of carbothermal reduction of quartz under vacuum.

Study of the kinetics of carbothermal reduction of quartz in a batch reactor between 0.25 torr and 1 microtorr. The effects of temperature, CO partial pressure, SiO2 phase transformation, and alkali and alkaline-earth oxide additives on the rate of reaction are reported. The results are consistent with a model based on a transitory phase intermediate.

Khalafalla, S. E.↗

The molecular velocity of sound

The molecular velocity of sound was calculated according to Rao's formula and the temperature and concentration dependences of this value were studied in aqueous solutions of alkali and alkaline-earth halides. Study of relative association brought to light characteristic effects of ions. The variation of the relative association can be explained by a breaking of hydrogen bonds by ions and thermal agitation.

Auslaender, D.↗

Internal pressures and molecular dimensions in aqueous solutions of some chlorides

On the basis of measurements of the velocity of ultrasounds in aqueous solutions of some alkaline-earth chlorides (MgCl2, CaCl2, BaCl2) the concentration and temperature dependences of the internal pressure were determined. Using these results, as well as surface tension measurements, the mean diameters of the molecular species as a function of concentration and temperature, were determined.

Auslaender, D.↗

Charge-transfer energy in closed-shell ion-atom interactions

The importance of charge-transfer energy in the interactions between closed-shell ions and atoms is investigated. Ab initio calculations on H(plus)-He and Li(plus)-He are used as a guide for the construction of approximate methods for the estimation of the charge-transfer energy for more complicated systems. For many alkali ion-rate gas systems the charge-transfer energy is comparable to the induction energy in the region of the potential minimum, although for doubly charged alkaline-earth ions in rare gases the induction energy always dominates. Surprisingly, an empirical combination of repulsion energy plus asymptotic induction energy plus asymptotic dispersion energy seems to give a fair representation of the total interaction, especially if the repulsion energy is parameterized, despite the omission of any explicit charge-transfer contribution. More refined interaction models should consider the charge-transfer energy contribution.

Alvarez-Rizzatti, M.↗

Economical synthesis of potassium superoxide

High-frequency discharge in oxygen can be used to prepare superoxides of alkali and alkaline-earth metals. Since no direct-current discharge at the electrodes is present, no sputtering can contaminate the product, hence a high conversion efficiency.

Bell, A. T.↗

On the origin of high-Ti mare basalts

Analyses were conducted of sixteen Apollo 17 mare basalts for alkali, alkaline-earth, and rare-earth elements, Co, and Sc. The obtained data were utilized in a study concerning the nature of the igneous processes responsible for the chemical variations among the high-Ti, low-K basalts. Estimates were obtained regarding the abundances of the large-ion, lithophile elements in the source regions for the basalts. It is shown that the source regions could plausibly have been produced by processes believed to have occurred during the early history of the moon. Attention is given to chemical variations among the Apollo 17 mare basalts, near-surface (low-pressure) crystal fractionation, partial melting, limits on the extent of partial melting, and a summary of possible events leading to formation of high-Ti mare basalts.

Shih, C.-Y.↗

Theoretical dissociation energies for ionic molecules

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Langhoff, S. R.↗