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At least 451 records · Page 25

Smectic pair-density-wave order in EuRbFe 4 As 4

The pair density wave (PDW) is a superconducting state in which Cooper pairs carry centre-of-mass momentum in equilibrium, leading to the breaking of translational symmetry. Experimental evidence for such a state exists in high magnetic field and in some materials that feature density-wave orders that explicitly break translational symmetry. However, evidence for a zero-field PDW state that exists independent of other spatially ordered states has so far been elusive. Here we show that such a state exists in the iron pnictide superconductor EuRbFe 4 As 4 , a material that features co-existing superconductivity (superconducting transition temperature ( T c ) ≈ 37 kelvin) and magnetism (magnetic transition temperature ( T m ) ≈ 15 kelvin). Using spectroscopic imaging scanning tunnelling microscopy (SI-STM) measurements, we show that the superconducting gap at low temperature has long-range, unidirectional spatial modulations with an incommensurate period of about eight unit cells. Upon increasing the temperature above Tm, the modulated superconductor disappears, but a uniform superconducting gap survives to T c . When an external magnetic field is applied, gap modulations disappear inside the vortex halo. The SI-STM and bulk measurements show the absence of other density-wave orders, indicating that the PDW state is a primary, zero-field superconducting state in this compound. FInally, both four-fold rotational symmetry and translation symmetry are recovered above T m , indicating that the PDW is a smectic order.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ion pair extractant selective for LiCl and LiBr

Improved methods for achieving the selective extraction of lithium salts from lithium sources, including rocky ores, salt-lake brines, and end-of-life lithium-ion batteries, could help address projected increases in the demand for lithium. Here, we report an ion pair receptor (2) capable of extracting LiCl and LiBr into an organic receiving phase both from the solid state and from aqueous solutions. Ion pair receptor 2 consists of a calix[4]pyrrole framework, which acts as an anion binding site, linked to a phenanthroline cation binding motif via ether linkages. Receptor 2 binds MgBr 2 and CaCl 2 with high selectivity over the corresponding lithium salts in a nonpolar aprotic solvent. The preference for Mg 2+ and Ca 2+ salts is reversed in polar protic media, allowing receptor 2 to complex LiCl and LiBr with high selectivity and affinity in organic media containing methanol or water. The effectiveness of receptor 2 as an extractant for LiCl and LiBr under liquid–liquid extraction (LLE) conditions was found to be enhanced by the presence of other potentially competitive salts in the aqueous source phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-scale electronic structure of the cuprate pair density wave state coexisting with superconductivity

In this work, by making a variety of quantitative comparisons between electronic visualization experiments and a theory describing coexisting pair density wave and superconductive states in cuprates, we find striking correspondence throughout. Therefore, our model can explain the microscopic origins of many key atomic-scale phenomena of the cuprate broken-symmetry state. These observations are consistent with the possibility that a short-range pair density wave (PDW) state coexists with superconductivity below a critical hole density in Bi 2 Sr 2 CaCu 2 O 8 , that the charge density wave modulations in cuprates are a consequence of the PDW state, that the cuprate pseudogap is the antinodal gap of the PDW, and that the critical point in the cuprate phase diagram occurs due to disappearance of the PDW.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analytic gradients for compressed multistate pair-density functional theory

Photochemical reactions often involve states that are closely coupled due to near degeneracies, for example by proximity to conical intersections. Therefore, a multistate method is used to accurately describe these states; for example, ordinary perturbation theory is replaced by quasidegenerate perturbation theory. Multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to approximate the full dynamical correlation energy of strongly correlated systems, and we recently proposed compressed multistate pair-density functional theory (CMS-PDFT) to treat closely coupled states. In the present paper, we report the implementation of analytic gradients for CMS-PDFT in both OpenMolcas and PySCF, and here we illustrate the use of these gradients by applying the method to the excited states of formaldehyde and phenol.

74 ATOMIC AND MOLECULAR PHYSICS↗

Dissociation dynamics of ion-pair states accessed by low-energy electron collisions

Abstract Ion-pair (IP) states are the superexcited states of the neutral molecule that dissociate as a pair of positive and negative ions. These states are generally present near the ionization continuum of the molecule. IP states can be accessed by using photoexcitation or by using the electron collision technique. Different photoexcitation techniques are widely used over the years to study the threshold (threshold IP production spectroscopy) and the dynamics (IP imaging spectroscopy) of the IP states. However, the electron collision technique is ignored over the years and only a few studies are available. In this review, we will discuss different experimental techniques to probe IP states by using electron collision and also the dynamics of the IP states that are accessed by the electron collision.

74 ATOMIC AND MOLECULAR PHYSICS↗

Effects of surface vacancy-adatom pair formation on PFC tungsten surface morphological response

Abstract We report a simulation study of the effect of He-irradiation-induced surface vacancy-adatom pair formation on the surface morphological evolution of plasma-facing component (PFC) tungsten and examine a number of factors that impact such evolution. Our analysis is based on self-consistent dynamical simulations according to an atomistically-informed, continuum-scale surface evolution model that has been developed following a hierarchical multiscale modeling strategy and can access the spatiotemporal scales of relevance to fuzz formation. The model accounts for the flux of surface adatoms generated as a result of the surface vacancy-adatom pair formation effect upon He implantation, which contributes to the anisotropic growth of surface nanostructural features due to the different rates of adatom diffusion along and across step edges of islands on the tungsten surface. We have carried out atomic-scale computations of optimal diffusion pathways along and across island step edges on the W(110) surface and calculated Ehrlich–Schwoebel (ES) barriers in adatom diffusion along and across such step edges. This aspect of surface adatom diffusion contributes to anisotropic surface atomic fluxes, terrace and step diffusive currents, and has been incorporated into our PFC surface evolution model, which predicts the formation of preferentially aligned nanoridge stripe patterns on the PFC surface. We establish that these anisotropic diffusive currents accelerate nanotendril growth on the PFC surface and the onset of surface nanostructure pattern formation. We also explore systematically the dependence of the PFC surface morphological response on the surface temperature and He ion incident flux, characterize in detail the resulting surface topographies and growth kinetics, and compare the predicted surface morphologies with experimental observations. Our simulation predictions for the emerging surface nanostructure patterns under certain plasma exposure conditions are consistent with experimental findings in the literature.

36 MATERIALS SCIENCE↗

Heralded Multiplexed High-Efficiency Cascaded Source of Dual-Rail Entangled Photon Pairs Using Spontaneous Parametric Down-Conversion

Deterministic sources of high-fidelity entangled qubit pairs encoded in the dual-rail photonic basis, i.e., presence of a single photon in one of two orthogonal modes, are a key enabling technology of many applications of quantum information processing, including high-rate, high-fidelity quantum communications over long distances. The most popular and mature sources of such photonic entanglement, e.g., those that leverage spontaneous parametric down-conversion (SPDC) or spontaneous four-wave mixing, generate an entangled (so-called continuous-variable) quantum state that contains contributions from high-order photon terms that lie outside the span of the dual-rail basis, which is detrimental to most applications. One often uses low pump power to mitigate the effects of those high-order terms. However, that reduces the pair generation rate, and the source becomes inherently probabilistic. We investigate a cascaded source that performs a linear-optical entanglement swap between two SPDC sources, to generate a heralded photonic entangled state that has a higher fidelity (to the ideal Bell state) compared to a free-running SPDC source. Furthermore, with the Bell swap providing a heralding trigger, we show how to build a multiplexed source, which despite reasonable switching losses and detector loss and noise, yields a fidelity versus success probability trade-off of a high-efficiency source of high-fidelity dual-rail photonic entanglement. We find, however, that there is a threshold of 1.5 dB of loss per switch, beyond which multiplexing hurts the fidelity versus success probability trade-off.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Twisted bilayer graphene. V. Exact analytic many-body excitations in Coulomb Hamiltonians: Charge gap, Goldstone modes, and absence of Cooper pairing

We find exact analytic expressions for the energies and wave functions of the charged and neutral excitations above the exact ground states (at rational filling per unit cell) of projected Coulomb Hamiltonians in twisted bilayer graphene. Our exact expressions are valid for any form of the Coulomb interaction and any form of A A and A B / B A tunneling. The single charge excitation energy is a convolution of the Coulomb potential with a quantum geometric tensor of the TBG bands. The neutral excitations are (high-symmetry group) magnons, and their dispersion is analytically calculated in terms of the form factors of the active bands in TBG. The two-charge excitation energy and wave functions are also obtained, and a sufficient condition on the graphene eigenstates for obtaining a Cooper pair from Coulomb interactions is obtained. For the actual TBG bands at the first magic angle, we can analytically show that the Cooper pair binding energy is zero in all such projected Coulomb models, implying that either phonons and/or nonzero kinetic energy are needed for superconductivity. Since Vafek and Kang [Phys. Rev. Lett. 125, 257602 (2020)] showed that the kinetic energy bounds on the superexchange energy are less 10 -3 in Coulomb units, the phonon mechanism becomes then very likely. If nonetheless the superconductivity is due to kinetic terms which render the bands nonflat, one prediction of our theory is that the highest T c would not occur at the highest DOS.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Orientational analysis of atomic pair correlations in nanocrystalline indium oxide thin films

The application of grazing-incidence total X-ray scattering (GITXS) for pair distribution function (PDF) analysis using >50 keV X-rays from synchrotron light sources has created new opportunities for structural characterization of supported thin films with high resolution. Compared with grazing-incidence wide-angle X-ray scattering, which is only useful for highly ordered materials, GITXS/PDFs expand such analysis to largely disordered or nanostructured materials by examining the atomic pair correlations dependent on the direction relative to the surface of the supporting substrate. A characterization of nanocrystalline In 2 O 3 -derived thin films is presented here with in-plane-isotropic and out-of-plane-anisotropic orientational ordering of the atomic structure, each synthesized using different techniques. The atomic orientations of such films are known to vary based on the synthetic conditions. Here, an azimuthal orientational analysis of these films using GITXS with a single incident angle is shown to resolve the markedly different orientations of the atomic structures with respect to the planar support and the different degrees of long-range order, and hence, the terminal surface chemistries. It is anticipated that orientational analysis of GITXS/PDF data will offer opportunities to extend structural analyses of thin films by providing a means to qualitatively determine the major atomic orientation within nanocrystalline and, eventually, non-crystalline films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Paired electrocatalysis in 5-hydroxymethylfurfural valorization

5-Hydroxymethylfurfural (HMF) has aroused considerable interest over the past years as an important biomass-derived platform molecule, yielding various value-added products. The conventional HMF conversion requires noble metal catalysts and harsh operating conditions. On the other hand, the electrocatalytic conversion of HMF has been considered as an environmentally benign alternative. However, its practical application is limited by low overall energy efficiency and incomplete conversion. Paired electrolysis and highly efficient electrocatalysts are two viable strategies to address these limitations. Herein, an overview of coupled electrocatalytic HMF hydrogenation or hydrogen evolution reaction (HER) with HMF oxidation as well as the associated electrocatalysts are reviewed and discussed. In this mini-review, a brief introduction of electrocatalytic HMF upgrading is given, followed by the recent advances and challenges of paired electrolysis with an emphasis on the integration HMF electrohydrogenation with HMF electrooxidation. Finally, a perspective for a future sustainable biomass upgrading community based on electrocatalysis is proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Searching for Pairs of Higgs Bosons in the LHC Run 2 Dataset

The discovery of the Higgs boson confirms the existence of a scalar sector of the standard model, responsible for electroweak symmetry breaking, but the nature and properties of the potential at the origin of this mechanism are still unknown. By studying the production of pairs of Higgs bosons (HH), physicists can directly measure the coupling of the Higgs boson to itself and thus determine the shape of this potential, which has far-reaching implications on the origin and evolution of our Universe. Because of this deep connection to the foundations of electroweak symmetry breaking, HH production is also an ideal place to search for manifestations of yet-unknown physics, such as modifications of the strength of the self-coupling and of the interaction between pairs of vector bosons and Higgs bosons. In this review article, we summarize the current searches for HH production at ATLAS and CMS, using the LHC Run 2 dataset, discuss the implications of our current constraints on physics beyond the standard model, and briefly review prospect for future HH searches.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Nucleon-Pair Shell Model within a Symmetry Broken Basis

The nucleon-pair shell model (NPSM) within the framework of a broken symmetry basis is studied. The results demonstrate the validity of such a scheme, which in turn leads to a significant reduction in the dimensionality of the multi-pair configuration space. Specifically, in the case of an axially-deformed basis, the results yield a satisfactory description of the low-lying spectrum, even without the need for applying the projection procedure. In the case of a triaxially-deformed basis, the result of variation after angular momentum projection suggest a potential for using the NPSM to find exact solutions in a semi-magic system.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Optimization of single-base-pair mismatch discrimination in oligonucleotide microarrays

The discrimination between perfect-match and single-base-pair-mismatched nucleic acid duplexes was investigated by using oligonucleotide DNA microarrays and nonequilibrium dissociation rates (melting profiles). DNA and RNA versions of two synthetic targets corresponding to the 16S rRNA sequences of Staphylococcus epidermidis (38 nucleotides) and Nitrosomonas eutropha (39 nucleotides) were hybridized to perfect-match probes (18-mer and 19-mer) and to a set of probes having all possible single-base-pair mismatches. The melting profiles of all probe-target duplexes were determined in parallel by using an imposed temperature step gradient. We derived an optimum wash temperature for each probe and target by using a simple formula to calculate a discrimination index for each temperature of the step gradient. This optimum corresponded to the output of an independent analysis using a customized neural network program. These results together provide an experimental and analytical framework for optimizing mismatch discrimination among all probes on a DNA microarray.

NASA Discipline Life Sciences Technologies↗

Single-base-pair discrimination of terminal mismatches by using oligonucleotide microarrays and neural network analyses

The effects of single-base-pair near-terminal and terminal mismatches on the dissociation temperature (T(d)) and signal intensity of short DNA duplexes were determined by using oligonucleotide microarrays and neural network (NN) analyses. Two perfect-match probes and 29 probes having a single-base-pair mismatch at positions 1 to 5 from the 5' terminus of the probe were designed to target one of two short sequences representing 16S rRNA. Nonequilibrium dissociation rates (i.e., melting profiles) of all probe-target duplexes were determined simultaneously. Analysis of variance revealed that position of the mismatch, type of mismatch, and formamide concentration significantly affected the T(d) and signal intensity. Increasing the concentration of formamide in the washing buffer decreased the T(d) and signal intensity, and it decreased the variability of the signal. Although T(d)s of probe-target duplexes with mismatches in the first or second position were not significantly different from one another, duplexes with mismatches in the third to fifth positions had significantly lower T(d)s than those with mismatches in the first or second position. The trained NNs predicted the T(d) with high accuracies (R(2) = 0.93). However, the NNs predicted the signal intensity only moderately accurately (R(2) = 0.67), presumably due to increased noise in the signal intensity at low formamide concentrations. Sensitivity analysis revealed that the concentration of formamide explained most (75%) of the variability in T(d)s, followed by position of the mismatch (19%) and type of mismatch (6%). The results suggest that position of the mismatch at or near the 5' terminus plays a greater role in determining the T(d) and signal intensity of duplexes than the type of mismatch.

Non-NASA Center↗

Degeneracy Removal of Spin Bands in Collinear Antiferromagnets with Non–Interconvertible Spin–Structure Motif Pair

Energy bands in antiferromagnets are supposed to be spin degenerate in the absence of spin–orbit coupling (SOC). Recent studies have identified formal symmetry conditions for antiferromagnetic crystals in which this degeneracy can be lifted, spin splitting, even in the vanishing SOC (i.e., non-relativistic) limit. Materials having such symmetries could enable spin-split antiferromagnetic spintronics without the burden of using heavy-atom compounds. However, the symmetry conditions that involve spin and magnetic symmetry are not always effective as practical material selection filters. Furthermore, these symmetry conditions do not readily disclose trends in the magnitude and momentum dependence of the spin-splitting energy. Here, it is shown that the formal symmetry conditions enabling spin-split antiferromagnets can be interpreted in terms of local motif pairs, such as octahedra or tetrahedra, each carrying opposite magnetic moments. Here, collinear antiferromagnets with such a spin-structure motif pair, whose components interconvert by neither translation nor spatial inversion, will show spin splitting. Such a real-space motif-based approach enables an easy way to identify and design materials (illustrated in real example materials) having spin splitting without the need for SOC, and offers insights into the momentum dependence and magnitude of the spin splitting.

36 MATERIALS SCIENCE↗

Synthesis of Zwitterionic CsPbBr 3 Nanocrystals with Controlled Anisotropy using Surface‐Selective Ligand Pairs

Abstract Mechanistic studies of the morphology of lead halide perovskite nanocrystals (LHP‐NCs) are hampered by a lack of generalizable suitable synthetic strategies and ligand systems. Here, the synthesis of zwitterionic CsPbBr 3 NCs is presented with controlled anisotropy using a proposed “surface‐selective ligand pairs” strategy. Such a strategy provides a platform to systematically study the binding affinity of capping ligand pairs and the resulting LHP morphologies. By using zwitterionic ligands (ZwL) with varying structures, majority ZwL‐capped LHP NCs with controlled morphology are obtained, including anisotropic nanoplatelets and nanorods, for the first time. Combining experiments with density functional theory calculations, factors that govern the ligand binding on the different surface facets of LHP‐NCs are revealed, including the steric bulkiness of the ligand, the number of binding sites, and the charge distance between binding moieties. This study provides guidance for the further exploration of anisotropic LHP‐NCs.

36 MATERIALS SCIENCE↗

Cation Migration in Physically Paired 2D and 3D Lead Halide Perovskite Films

2D/3D interfaces provide long-term stability for the operation of metal halide perovskite solar cells. However, the cation migration under heat and light can disturb the interface and create a graded cation interface. This study has now probed the cation migration by physically pairing X 2 PbI 4 (X = butylammonium BA, oleylammonium OA, or phenethylammonium PEA) 2D film and (CH 3 NH 3 , MA)PbI 3 3D film at different temperatures and recording changes in the absorption and emission spectra. The migration of the methyl ammonium cation toward the 2D film slowly transforms the n = 1 layered phase into n = 2 and 3 layered phases. The 3D film, on the other hand, exhibits relatively small changes, as the inclusion of spacer cation has little effect on its phase. The apparent activation energy determined from the temperature-dependent cation migration kinetics (E a = 29– 50 kJ mol –1 ) indicates alkyl ammonium cations such as butyl ammonium migrate more readily into the 3D layer than aromatic cations such as PEA. As a result, the ease of migration of spacer cations between physically paired films suggests that the varied composition at the interface should be considered while evaluating the effectiveness of the 2D/3D design strategy for improving the performance of perovskite solar cells.

2D/3D perovskite↗

Light–Induced Frenkel Defect Pair Formation Can Lead to Phase–Segregation of Otherwise Miscible Halide Perovskite Alloys

Alloys of ABX 3 halide perovskites (HP) exhibit unique phase behavior compared to traditional III-V and II-VI semiconductor alloys used in solar cells. While the latter typically have good mutual miscibility when their mixed components are size matched, and phase-segregate when size mismatched, HP alloys show good miscibility in the dark but can phase-segregate under light. Quantum mechanical calculations described herein reveal light-induced defect formation and migration hold the key. Specifically, the interaction between a halogen vacancy V X with halogen interstitial X i forming together a Frenkel-pair defect emerges as the enabler for phase-segregation in HP alloys. At a threshold bromine composition in the Br-I alloys, the photogenerated holes in the valence band localize, creating thereby a doubly-charged iodine Frenkel-pair (V I + I i ) 2+ . Faster migration of iodine over bromine interstitial into the vacant iodine V I site leads to the formation of iodine-rich and iodine-depleted regions, establishing phase-segregation. Removal of the mobile defects–the agent of segregation–by dark thermal annealing, supplies the opposing force, leading to reversal of phase-segregation. Furthermore, this atomistic understanding can enable some control of the phase-segregation by selecting substituting elements on the B site–such as replacing some Pb by Sn–that are unable to form stable Frenkel defects.

14 SOLAR ENERGY↗