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At least 1,657 records · Page 92

A two-dimensional numerical study of ion-acoustic turbulence

We investigate the linear and nonlinear evolution of the current-driven ion-acoustic instability in a collisionless plasma via two-dimensional (2-D) Vlasov–Poisson numerical simulations. We initialise the system in a stable state and gradually drive it towards instability with an imposed, weak external electric field, thus avoiding physically unrealisable super-critical initial conditions. A comprehensive analysis of the nonlinear evolution of ion-acoustic turbulence (IAT) is presented, including the detailed characteristics of the evolution of the particles’ distribution functions, (2-D) wave spectrum and the resulting anomalous resistivity. Our findings reveal the dominance of 2-D quasi-linear effects around saturation, with nonlinear effects, such as particle trapping and nonlinear frequency shifts, becoming pronounced during the later stages of the system's nonlinear evolution. Remarkably, the Kadomtsev–Petviashvili (KP) spectrum is observed immediately after the saturation of the instability. Another crucial and noteworthy result is that no steady saturated nonlinear state is ever reached: strong ion heating suppresses the instability, which implies that the anomalous resistivity associated with IAT is transient and short-lived, challenging earlier theoretical results. Towards the conclusion of the simulation, electron-acoustic waves are triggered by the formation of a double layer and strong modifications to the particle distribution induced by IAT.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

An Empirical Model of Radiation Belt Electron Pitch Angle Distributions Based On Van Allen Probes Measurements

Based on over 4 years of Van Allen Probes measurements, an empirical model of radiation belt electron equatorial pitch angle distribution (PAD) is constructed here. The model, developed by fitting electron PADs with Legendre polynomials, provides the statistical PADs as a function of L-shell (L = 1–6), magnetic local time, electron energy (~30 keV to 5.2 MeV), and geomagnetic activity (represented by the Dst index) and is also the first empirical PAD model in the inner belt and slot region. For megaelectron volt electrons, model results show more significant day-night PAD asymmetry of electrons with higher energies and during disturbed times, which is caused by geomagnetic field configuration and flux radial gradient changes. Steeper PADs with higher fluxes around 90° pitch angle and lower fluxes at lower pitch angles for higher-energy electrons and during active times are also present, which could be due to electromagnetic ion cyclotron wave scattering. For hundreds of kiloelectron volt electrons, cap PADs are generally present in the slot region during quiet times and their energy-dependent features are consistent with hiss wave scattering, while during active times, cap PADs are less significant especially at outer part of slot region, which could be due to the complex energizing and transport processes. Finally, the 90°-minimum PADs are persistently present in the inner belt and appear in the slot region during active times, and minima at 90° pitch angle are more significant for electrons with higher energies, which could be a critical evidence in identifying the underlying physical processes responsible for the formation of 90°-minimum PADs.

79 ASTRONOMY AND ASTROPHYSICS↗

Magic-angle semimetals

Abstract Breakthroughs in two-dimensional van der Waals heterostructures have revealed that twisting creates a moiré pattern that quenches the kinetic energy of electrons, allowing for exotic many-body states. We show that cold atomic, trapped ion, and metamaterial systems can emulate the effects of a twist in many models from one to three dimensions. Further, we demonstrate at larger angles (and argue at smaller angles) that by considering incommensurate effects, the magic-angle effect becomes a single-particle quantum phase transition (including in a model for twisted bilayer graphene in the chiral limit). We call these models “magic-angle semimetals”. Each contains nodes in the band structure and an incommensurate modulation. At magic-angle criticality, we report a nonanalytic density of states, flat bands, multifractal wave functions that Anderson delocalize in momentum space, and an essentially divergent effective interaction scale. As a particular example, we discuss how to observe this effect in an ultracold Fermi gas.

Materials Science↗

NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of shock roughness due to phase plate speckle imprinting relevant for x-ray diffraction experiments on 3rd and 4th generation light sources

Laser-shock compression experiments at 3rd and 4th generation light sources generally employ phase plates, which are inserted into the beamline to achieve a repeatable intensity distribution at the focal plane. Here, the laser intensity profile is characterized by a high-contrast, high-frequency laser speckle. Without sufficient smoothing, these laser non-uniformities can translate to a significant pressure distribution within the sample layer and can affect data interpretation in x-ray diffraction experiments. Here, we use a combination of one- and two-dimensional velocity interferometry to directly measure the extent to which spatial frequencies within the laser focal spot intensity pattern are smoothed out during propagation within the laser plasma and a polyimide ablator. We find that the use of thicker polyimide layers results in spatially smoother shock fronts, with the greatest degree of smoothing associated with the highest spatial frequencies. Focal spots with the smallest initial speckle separation produce the most rapid smoothing. Laser systems that employ smoothing by spectral dispersion techniques to rapidly modulate the focal plane intensity distribution are shown to be the most effective ones in producing a spatially smooth shock front. We show that a simple transport model combined with the known polyimide Hugoniot adequately describes the extent of shock smoothness as a function of polyimide thickness. Finally, our results provide a description of spatial structure smoothing across a shock front, which can be used to design targets on x-ray free electron laser facilities.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A Systematic, Polynomial-Cost Approach to Exact Correlation Energies (Final Technical Report)

The full configuration interaction (FCI) wave function provides the exact solution to the Schrödinger equation in a given basis set. While FCI is intractable due to exponential computational costs, the many-body expansion (or the method of increments) can reduce scaling to a low-order polynomial with system size. This project entailed advances in the incremental FCI (iFCI) approach, designed to allow iFCI to reach larger system sizes and maintain its intrinsic high accuracy. This document describes advances in solvers for iFCI, strategies to treat multiple charge and spin states, and virtual state management methods to reduce memory requirements. Overall, this project allows iFCI to correlate (for the first time) 142 valence electrons in 444 orbitals in a realistic model of a transition metal complex.

74 ATOMIC AND MOLECULAR PHYSICS↗

Fermi level tuning and double-dome superconductivity in the kagome metal CsV 3 Sb 5 – x Sn x

The recently reported AV 3 Sb 5 (A = K , Rb, Cs) family of kagome metals are candidates for unconventional superconductivity and chiral charge density wave (CDW) order; both potentially arise from nested saddle points in their band structures close to the Fermi energy. Here, we use chemical substitution to introduce holes into CsV 3 Sb 5 and unveil an unconventional coupling of the CDW and superconducting states. Specifically, we generate a phase diagram for CsV 3 Sb 5 – x Sn x that illustrates the impact of hole doping the system and lifting the nearest van Hove singularity toward and above E F . Superconductivity exhibits a nonmonotonic evolution with the introduction of holes, resulting in two “domes” peaked at 3.6 and 4.1 K and the rapid suppression of three-dimensional CDW order. Further, the evolution of CDW and superconducting order is compared with the evolution of the electronic band structure of CsV 3 Sb 5 – x Sn x , where the complete suppression of superconductivity seemingly coincides with an electronlike band comprised of Sb p z orbitals pushed above E F .

36 MATERIALS SCIENCE↗

A novel conditional formulation of the Vlasov–Ampère equations: a conservative, positivity, asymptotic and Gauss law preserving scheme

We propose a novel reformulation of the Vlasov–Ampère equations for plasmas that reveals discrete symmetries that enables simultaneous conservation of mass, momentum and energy; preservation of Gauss’s law; positivity of the distribution function; and consistency with quasi-neutral asymptotics. The approach employs variable and coordinate transformations to yield a coupled system comprising a modified Vlasov equation and associated moment–field equations. The modified Vlasov equation advances a conditional distribution function that excludes mass, momentum and energy densities, which are instead evolved through moment equations enforcing the relevant symmetries, conservation laws and involution constraints. This reformulation aligns naturally with a recent slow-manifold reduction technique, which separates fast electron time scales and simplifies the treatment of the quasi-neutral limit within the reduced moment–field subsystem. Using this framework, we develop a numerical method for the reduced 1D1V subsystem that, for the first time in the literature, satisfies all key physical constraints while maintaining a quasi-neutral asymptotic behaviour. The advantages of the method are demonstrated on canonical electrostatic test problems, including the multiscale ion acoustic shock wave.

1D1V↗

Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

The computational investigation of the molecular geometries of a pair of manganese(III) spin-crossover complexes is reported. For the geometry of the quintet high-spin state, density functionals significantly overestimate Mn–Namine bond distances, although the geometry for the triplet intermediate-spin state is well described. Here, comparisons with several wave function-based methods demonstrate that this error is due to the limited ability of commonly used density functionals to recover dispersion beyond a certain extent. Among the methods employed for geometry optimization, restricted open-shell Møller–Plesset perturbation theory (MP2) appropriately describes the high-spin geometry but results in a slightly shorter Mn–O distance in both spin states. On the other hand, extended multistate complete active space second-order perturbation theory (XMS-CASPT2) provides a good description of the geometry for the intermediate-spin state but also sufficiently recovers dispersion, performing well for the high-spin state. Despite the fact that the electronic structure of both spin states is dominated by one-electron configuration, XMS-CASPT2 offers a balanced approach, leading to molecular geometries with much better agreement with experiment than MP2 and DFT. A scan along the Mn–N amine bond demonstrates that for these complexes coupled cluster methods (i.e., DLPNO-CCSD(T)) also yield bond distances in agreement with experiment while multiconfiguration pair density functional theory (MC-PDFT) is unable to recover dispersion well enough, analogous to single-reference DFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inducing metallicity in graphene nanoribbons via zero-mode superlattices

The design and fabrication of robust metallic states in graphene nanoribbons (GNRs) are challenging because lateral quantum confinement and many-electron interactions induce electronic band gaps when graphene is patterned at nanometer length scales. Recent developments in bottom-up synthesis have enabled the design and characterization of atomically precise GNRs, but strategies for realizing GNR metallicity have been elusive. Here we demonstrate a general technique for inducing metallicity in GNRs by inserting a symmetric superlattice of zero-energy modes into otherwise semiconducting GNRs. We verify the resulting metallicity using scanning tunneling spectroscopy as well as first-principles density-functional theory and tight-binding calculations. Our results reveal that the metallic bandwidth in GNRs can be tuned over a wide range by controlling the overlap of zero-mode wave functions through intentional sublattice symmetry breaking.

36 MATERIALS SCIENCE↗

Two-Dimensional Moiré Polaronic Electron Crystals

Two-dimensional moiré materials have emerged as the most versatile platform for realizing quantum phases of electrons. Here, we explore the stability origins of correlated states in WSe 2 /WS 2 moiré superlattices. We find that ultrafast electronic excitation leads to partial melting of the Mott states on timescales 5 times longer than predictions from the charge hopping integrals and that the melting rates are thermally activated, with activation energies of 1⁢8±3 and 1⁢3±2 meV for the one- and two-hole Mott states, respectively, suggesting significant electron-phonon coupling. A density functional theory calculation of the one-hole Mott state confirms polaron formation and yields a hole-polaron binding energy of 16 meV. These findings reveal a close interplay of electron-electron and electron-phonon interactions in stabilizing the polaronic Mott insulators at transition metal dichalcogenide moiré interfaces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Topics in Theoretical Physics

This award supported a broadly based research effort in theoretical particle physics, including research aimed at uncovering the laws of nature at short (subatomic) and long (cosmological) distances. These theoretical developments apply to experiments in laboratories such as CERN, the facility that operates the Large Hadron Collider outside Geneva, as well as to cosmological investigations done using telescopes and satellites. The results reported here apply to physics beyond the so-called Standard Model of particle physics; physics of high energy collisions such as those observed at the Large Hadron Collider; theoretical and mathematical tools and frameworks for describing the laws of nature at short distances; cosmology and astrophysics; and analytic and computational methods to solve theories of short distance physics. Some specific research accomplishments include + Theories of the electroweak interactions, the forces that give rise to many forms of radioactive decay; + Physics of the recently discovered Higgs boson. + Models and phenomenology of dark matter, the mysterious component of the universe, that has so far been detected only by its gravitational effects. + High energy particles in astrophysics and cosmology. + Algorithmic research and Computational methods for physics of and beyond the Standard Model. + Theory and applications of relativity and its possible limitations. + Topological effects in field theory and cosmology. + Conformally invariant systems and AdS/CFT. This award also supported significant training of students and postdoctoral fellows to lead the research effort in particle theory for the coming decades. These students and fellows worked closely with other members of the group as well as theoretical and experimental colleagues throughout the physics community. Many of the research projects funded by this grant arose in response to recently obtained experimental results in the areas of particle physics and cosmology. We describe a few of these below. Relativity is founded on a symmetry property of nature called "Lorentz Invariance". Like all symmetry properties, it is essential to determine precisely how symmetric nature actually is; that is, do the laws of nature fully respect the symmetry or is there room for tiny symmetry violating effects? An important consequence of Lorentz invariance is the existence of a universal limiting velocity for all physical particles. Light travels at this limiting velocity so it is frequently referred to as simply "the speed of light", but relativity requires that ALL particles travel more slowly than this speed. Once the Higgs particle was discovered in 2012 a natural question was whether or not this particle's speed was consistent with relativity. Although the speed of the Higgs particle is not measurable directly, Cohen has shown that, if the maximal speed of the Higgs particle was not precisely the same as the speed of light, then the Higgs would have some unusual properties. In some cases the Higgs would be unstable to some unusual decay modes; in other cases the interactions of the Higgs with other particles would change the properties of these other particles in ways that could be observed in so-called cosmic rays, very energetic particles (such as photons, protons and other atomic nuclei) coming from space. Once these particles hit the upper atmosphere they produce a "shower" of particles that can be seen by ground-based instruments. If the Higgs has a maximal speed that differs even a tiny bit from the speed of light these showers would look quite different from what is observed. In this way Cohen was able to establish that the Higgs travels with a maximal speed that cannot differ from the speed of light by more than one part in a thousand-trillion. This is by far the most precisely determined property of the Higgs particle. Cohen and Schmaltz reviewed evidence from the Large Hadron Collider (LHC), a particle physics experiment operating at the CERN laboratory near Geneva, for a new particle sometimes called a W'. This evidence included certain unexpected by-products in collisions of protons at very high energy. While the evidence was not significant enough to claim a discovery, it was sufficiently intriguing that many particle theorists worked to construct explanations for this signal. Cohen and Schmaltz were able to determine that such explanations are highly constrained by previous experiments involving collisions of very energetic particles. Nevertheless they were able to construct a theory that adequately explains the LHC data and remain consistent with prior experiments. Their explanation predicts the existence of yet another new particle, called a Z', with a mass slightly greater than that of the W'. This additional particle, if it exists, should be seen as more data is collected from the LHC. Amusingly, there is one collision by-product that has already been seen by the CMS experiment at the LHC that supports the existence of this new particle; however, it is not unlikely that this single event is a so-called "background" event, that is a somewhat atypical by-product of a conventional Standard Model process. This theory for the anomalous LHC data will either be confirmed or excluded with further data-taking at the LHC. The ratio of the number of electrons produced in bottom quark decays over the number of muons produced has been measured at the LHC. This ratio is interesting because it can be predicted very precisely from a basic property of the Standard Model: lepton universality. If lepton universality is correct, the ratio of electrons to muons is predicted to be equal to 1. The first measurements of this ratio find a value different from 1 with a statistical significance of about 3 standard deviations. Schmaltz and collaborator proposed a new extension of the Standard Model which can explain the new data. In addition, Schmaltz and collaborators proposed several new measurements of ratios of decay rates which can confirm or rule out the surprising results from the earlier LHC data. The most recent and precise measurements of the cosmic microwave background from the Planck satellite, from a combination of measurements of the dark matter distribution in the universe, and from a measurement of the expansion rate of the universe today show some disagreement when interpreted in terms of the so-called LambdaCDM model. Schmaltz and collaborators proposed an alternative model to LambdaCDM in which the usual cold dark matter is replaced by a new ``dark sector". This sector consists of a cold dark matter particle which interacts with a newly postulated dark radiation component of the universe. The dark radiation can help explain the discrepancy in measurements of the expansion rate, and the dark matter interactions subtly modify the clumping of dark matter at large scales, thus potentially explaining both kinds of tensions in the data. In two publications Schmaltz described the new model and then performed a precision comparison of the predictions of the model with all currently available cosmological data. The results favor the new model at the level of three standard deviations with current data. Quantum Field Theory (QFT) is the language we use to describe quantum systems which are consistent with Einstein’s theory of Special Relativity. In particular, the requirement of Einstein’s theory that signals not travel faster than the speed of light constrains the types of interactions which particles can engage in. One consequence of relativity is that these interactions cannot preserve particle number. The stronger the interactions, the more severe the particle number violation in a given Relativistic QFT. When particle number violation is strong, it becomes very difficult to adequately parameterize the quantum wave function (which characterizes the state of a quantum system). For example, though we can formulate the QFT which describes the strong force as a set of interactions between quark and gluon particles, we have no clear idea how to express the proton state in terms of these quarks and gluons. This is because the proton, though a bound state of quarks and gluons, is not a state of a fixed number of particles due to strong interactions. Yet, understanding the proton state is very important in order to theoretically predict the reaction rates observed at the LHC in Geneva, which is a proton-proton collider. Katz has formulated a new approach to QFT, which among other things offers a way to adequately approximate the quantum wave function of a bound state at strong coupling. The approximation scheme is related to the fact that any sensible QFT (including that of the strong interactions) is at short distances approximately self-similar upon rescaling of space and time. It turns out that keeping track of the response upon this rescaling is important in efficiently parameterizing the state. Katz and collaborators have used this observation to approximate the state of the proton in toy versions of the strong force. In the late 60s Sheldon Glashow, Abdus Salam and Steven Weinberg (1979 Nobel Prize awardees) proposed a theory unifying weak and electromagnetic interaction which assumed the existence of new particles, the W and Z bosons. The W and Z bosons were eventually detected in high-energy collision in a particle accelerator at CERN, and the recent discovery of the Higgs meson at the Large Hadron Collider (LHC), always at CERN, completed the picture. However, deep theoretical considerations indicate that the theory by Glashow, Weinberg and Salam, often referred to as "the standard model" cannot be the whole story: the existence of new particles and new interactions at yet higher energies is widely anticipated. The experiments at the LHC are looking for these, while theorists, like Brower, Rebbi and collaborators, are investigating models for these new interactions. Working in a large national collaboration with access to the most powerful DOE computers Brower, Rebbi and colleagues have been using calculational techniques, similar to those successfully employed for many years to investigate the interactions among quarks in nucleons, to study theories that can describe the expected "beyond the standard model" (BSM) interactions. Their results, which include also a model for dark matter, have been published in several refereed papers in prestigious journals. Various ideas in topologically interesting field theories predict hypothetical objects such as fractional charges and Majorana excitations. However, such fascinating objects have not been seen in particle physics. Nevertheless, these objects demonstrate possible phenomena that quantum field theory can support. Pi used condensed matter physics as a laboratory to study possible realizations and observable effects of these objects predicted by quantum field theory. In recent times there has developed considerable interest among condensed matter field theorists in precisely the same geometrical and topological structures, which were first discovered in particle physics field theories. From particle physicists' point of view, this is an interesting development, since condensed matter provides an arena in which one can concretely realize particle physics ideas. Moreover, particle physicists can learn new ideas from condensed matter physics. Higgs phenomenon is precisely an important particle physics realization of condensed matter ideas. In contrast to the small distance characterizing condensed matter systems, field theory also describes large distance physics characterizing cosmology. Pi worked on various geometrical effects in the standard theory of cosmology, viz general relativity.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Starting-point-independent quantum Monte Carlo calculations of iron oxide

Quantum Monte Carlo (QMC) methods are useful for studies of strongly correlated materials because they are many body in nature and use the physical Hamiltonian. Typical calculations assume as a starting point a wave function constructed from single-particle orbitals obtained from one-body methods, e.g., density functional theory. However, mean-field-derived wave functions can sometimes lead to systematic QMC biases if the mean-field result poorly describes the true ground state. In this study, we examine the accuracy and flexibility of QMC trial wave functions using variational and fixed-node diffusion QMC estimates of the total spin density and lattice distortion of antiferromagnetic iron oxide (FeO) in the ground state B1 crystal structure. We found that for relatively simple wave functions the predicted lattice distortion was controlled by the choice of single-particle orbitals used to construct the wave function, rather than by subsequent wave function optimization techniques within QMC. By optimizing the orbitals with QMC, we then demonstrate starting-point independence of the trial wave function with respect to the method by which the orbitals were constructed by demonstrating convergence of the energy, spin density, and predicted lattice distortion for two qualitatively different sets of orbitals. The results suggest that orbital optimization is a promising method for accurate many-body calculations of strongly correlated condensed phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Real-time time-dependent density functional theory in Quantum Espresso and related codes

A set of subroutines that interact with an existing computer program, Quantum Espresso (QE), that takes a set of electronic orbitals from QE and propagates them forward in time in response to a number of perturbations. These perturbations include the motion of ions and a wide spectrum of applied electromagnetic fields (e.g., static magnetic fields, slowly-varying electric fields, x-rays, etc.). From the time evolution of the electronic orbitals comes time-varying values of physical observables like the electronic charge and current densities and atomic forces. These are further post-processed to yield properties of interest like stopping powers, conductivities, and the dynamic structure factor. The electronic orbitals are described in a plane wave basis and the equations of motion are carried out using a unitary or approximately unitary time propagation algorithm. Related work will include subroutines for interfacing this capability, as well as others that already exist within QE, with a fork of QE that is more extensible and modular.SAND2019-12611 M Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

Baczewski, Andrew↗

Intercalation induced quasi-freestanding layer in TiSe 2

Angle-resolved photoemission spectroscopy is employed to study the electronic structure of bulk TiSe 2 before and after doping with potassium impurities. A splitting in the conduction band into two branches is observed after room-temperature deposition. The splitting energy increases to approximately 130 meV when the sample is cooled to 40 K. One branch exhibits a nondispersive two-dimensional feature, while the other shows the characteristics of three-dimensional bulk band dispersion. Core-level spectroscopy suggests that the K impurities predominantly occupy the intercalated sites within the van der Waals gap. Furthermore, the results indicate the formation of a quasi-freestanding TiSe 2 layer. Additionally, doping completely suppresses the periodic lattice distortion in the surface region. These findings are further supported by density functional theory calculations, which compare the band structure of monolayer and bulk TiSe 2 with experimental data. Thus, the dimensional and intrinsic electronic properties of 1⁢𝑇−TiSe 2 can be controlled through the intercalation procedure used in this work.

36 MATERIALS SCIENCE↗

Yttria-Stabilized Zirconia Aided Electrochemical Investigation on Ferric Ions in Mixed Molten Calcium and Sodium Chlorides

Electrolytic reduction of dissolved iron oxide to metal iron in molten salts with an inert anode is an alternative short route for steelmaking without CO{sub 2} emissions. A novel and simple integrated yttria-stabilized zirconia (YSZ) cell was constructed from a YSZ tube with a closed end. The YSZ tube played multiple functions, including the container for the molten salts, the solid electrolyte membrane in the O{sup 2−}|YSZ|Pt|O{sub 2} (air) reference electrode (RE), and the solid electrolyte membrane between the working and counter electrodes (WE and CE). Electrochemical behavior of ferric ions (Fe{sup 3+}) that were formed by dissolution of 0.5 wt pct Fe{sub 2}O{sub 3} in the molten CaCl{sub 2}-NaCl eutectic mixture was investigated on a Pt WE at 1273 K by various electrochemical techniques including cyclic voltammetry, linear scan voltammetry, square wave voltammetry, chronopotentiometry, chronoamperometry, and potentiostatic electrolysis. Analysis of the mechanism of electrode reactions was further assisted by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Some electrochemical parameters were obtained, including the number of exchanged electrons and the diffusion coefficient of ferric ions in the mixed molten salts. The results from various electrochemical techniques are in good agreement with each other, and show that the electrochemical reduction of Fe{sup 3+} to Fe in the molten salt mixture could be a single three-electron transfer step and diffusion-controlled reaction that was also possibly reversible. This work may form the foundation for extraction of iron and alloys from molten salts and also provide a stable O{sup 2−}|YSZ|Pt|O{sub 2} (air) RE with wide applicability for investigation on electrochemical properties of other electroactive metal oxides in molten salts.

36 MATERIALS SCIENCE↗

Modeling light-induced charge transfer dynamics across a metal-molecule-metal junction: Bridging classical electrodynamics and quantum dynamics

We develop a numerical approach for simulating light-induced charge transport dynamics across a metal-molecule-metal conductance junction. The finite-difference time-domain method is used to simulate the plasmonic response of the metal structures. The Huygens subgridding technique, as adapted to Lorentz media, is used to bridge the vastly disparate length scales of the plasmonic metal electrodes and the molecular system, maintaining accuracy. The charge and current densities calculated with classical electrodynamics are transformed to an electronic wavefunction, which is then propagated through the molecular linker via the Heisenberg equations of motion. We focus mainly on development of the theory and exemplify our approach by a numerical illustration of a simple system consisting of two silver cylinders bridged by a three-site molecular linker. The electronic subsystem exhibits fascinating light driven dynamics, wherein the charge density oscillates at the driving optical frequency, exhibiting also the natural system timescales, and a resonance phenomenon leads to strong conductance enhancement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cost-effective description of strong correlation: Efficient implementations of the perfect quadruples and perfect hextuples models

Novel implementations based on dense tensor storage are presented here for the singlet-reference perfect quadruples (PQ) [J. A. Parkhill et al., J. Chem. Phys. 130, 084101 (2009)] and perfect hextuples (PH) [J. A. Parkhill and M. Head-Gordon, J. Chem. Phys. 133, 024103 (2010)] models. The methods are obtained as block decompositions of conventional coupled-cluster theory that are exact for four electrons in four orbitals (PQ) and six electrons in six orbitals (PH), but that can also be applied to much larger systems. PQ and PH have storage requirements that scale as the square, and as the cube of the number of active electrons, respectively, and exhibit quartic scaling of the computational effort for large systems. Applications of the new implementations are presented for full-valence calculations on linear polyenes (C n H n+2 ), which highlight the excellent computational scaling of the present implementations that can routinely handle active spaces of hundreds of electrons. The accuracy of the models is studied in the π space of the polyenes, in hydrogen chains (H 50 ), and in the π space of polyacene molecules. In all cases, the results compare favorably to density matrix renormalization group values. With the novel implementation of PQ, active spaces of 140 electrons in 140 orbitals can be solved in a matter of minutes on a single core workstation, and the relatively low polynomial scaling means that very large systems are also accessible using parallel computing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗