Enhanced Twist-Averaging Technique for Magnetic Metals: Applications Using Quantum Monte Carlo.

We propose an improved twist-averaging (TA) scheme for quantum Monte Carlo methods that use converged Kohn-Sham or Hartree-Fock orbitals as the reference. This TA technique is tailored to sample the Brillouin zone of magnetic metals, although it naturally extends to nonmagnetic (NM) conducting systems. The proposed scheme aims to reproduce the reference magnetization and achieves charge neutrality by construction, thus avoiding the large energy fluctuations and the postprocessing needed to correct the energies. It shows the most robust convergence of total energy and magnetism to the thermodynamic limit (TDL) when compared to four other TA schemes. Diffusion Monte Carlo applications are shown on NM Al and ferromagnetic α-Fe. The cohesive energy of Al in the TDL shows an excellent agreement with the experimental result. Furthermore, the magnetic moments in α-Fe exhibit rapid convergence with an increasing number of twists.

A new generation of effective core potentials: Selected lanthanides and heavy elements.

We construct correlation-consistent effective core potentials (ccECPs) for a selected set of heavy atoms and f elements that are currently of significant interest in materials and chemical applications, including Y, Zr, Nb, Rh, Ta, Re, Pt, Gd, and Tb. As is customary, ccECPs consist of spin-orbit (SO) averaged relativistic effective potential (AREP) and effective SO terms. For the AREP part, our constructions are carried out within a relativistic coupled-cluster framework while also taking into account objective function one-particle characteristics for improved convergence in optimizations. The transferability is adjusted using binding curves of hydride and oxide molecules. We address the difficulties encountered with f elements, such as the presence of large cores and multiple near-degeneracies of excited levels. For these elements, we construct ccECPs with core-valence partitioning that includes 4f subshell in the valence space. The developed ccECPs achieve an excellent balance between accuracy, size of the valence space, and transferability and are also suitable to be used in plane wave codes with reasonable energy cutoffs.

DFT+U and quantum Monte Carlo study of electronic and optical properties of AgNiO2 and AgNi1-xCoxO2 delafossite.

As the only semimetallic d10-based delafossite, AgNiO2 has received a great deal of attention due to both its unique semimetallicity and its antiferromagnetism in the NiO2 layer that is coupled with a lattice distortion. In contrast, other delafossites such as AgCoO2 are insulating. Here we study how the electronic structure of AgNi1-xCoxO2 alloys vary with Ni/Co concentration, in order to investigate the electronic properties and phase stability of the intermetallics. While the electronic and magnetic structure of delafossites have been studied using density functional theory (DFT), earlier studies have not included corrections for strong on-site Coulomb interactions. In order to treat these interactions accurately, in this study we use Quantum Monte Carlo (QMC) simulations to obtain accurate estimates for the electronic and magnetic properties of AgNiO2. By comparison to DFT results we show that these electron correlations are critical to account for. We show that Co doping on the magnetic Ni sites results in a metal-insulator transition near x ∼0.33, and reentrant behavior near x ∼ 0.66.

Stacking Faults and Topological Properties in MnBi2Te4: Reconciling Gapped and Gapless States.

Despite theoretical predictions of a gapped surface state for the magnetic topological insulator MnBi2Te4 (MBT), there has been a series of experimental evidence pointing toward gapless states. Here, we theoretically explore how stacking faults could influence the topological characteristics of MBT. We envisage a scenario that a stacking fault exists at the surface of MBT, causing the uppermost layer to deviate from the ground state and its interlayer separation to be expanded. This stacking fault with modulated interlayer couplings hosts a nearly gapless state within the topmost layer due to charge redistribution as the outermost layer recedes. Furthermore, we find evidence of spin-momentum locking and preservation of weak band inversion in the gapless surface state, suggesting the nontrivial topological surface states in the presence of the stacking fault. Our findings provide a plausible elucidation to the long-standing conundrum of reconciling the observation of gapped and gapless states on MBT surfaces.

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO2.

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. This high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

Deterministic Conductive Filament Formation and Evolution for Improved Switching Uniformity in Embedded Metal-Oxide-Based Memristors─A Phase-Field Study.

The extreme device-to-device variation of switching performance is one of the major obstacles preventing the applications of metal-oxide-based memristors in large-scale memory storage and resistive neural networks. Recent experimental works have reported that embedding metal nano-islands (NIs) in metal oxides can effectively improve the uniformity of the memristors, but the underlying role of the NIs is not fully understood. Here, to address this specific problem, we develop a physical model to understand the origin of the variability and how the embedded NIs can improve the performance and uniformity of memristors. We find that due to the dimension confinement effect, embedding metal NIs can modulate the electric field distribution and lead to a more deterministic formation of the conductive filament (CF) from their vicinity, in contrast to the random growth of CFs without embedded NIs. This deterministic CF formation, via vacancy nucleation, further reduces the forming, reset, and set voltages and enhances the uniformity of the operation voltages and current ON/OFF ratios. We further demonstrate that modifying the shapes of the metal NIs can modulate the field strengths/distributions around the NIs and that choosing the NI metal composition and shape that chemically facilitate vacancy formations can further optimize the CF morphology, reduce the operation voltages, and improve the switching performance. Our work thus provides a fundamental understanding of how embedded metal NIs improve the resistive switching performance in oxide-based memristors and could potentially guide the selection of embedded NIs to realize a more uniform memristor that also operates at a higher efficiency than present materials.

Extraction of interaction parameters from specular neutron reflectivity in thin films of diblock copolymers: an "inverse problem".

Diblock copolymers have been shown to undergo microphase separation due to an interplay of repulsive interactions between dissimilar monomers, which leads to the stretching of chains and entropic loss due to the stretching. In thin films, additional effects due to confinement and monomer-surface interactions make microphase separation much more complicated than in that in bulks (i.e., without substrates). Previously, physics-based models have been used to interpret and extract various interaction parameters from the specular neutron reflectivities of annealed thin films containing diblock copolymers (J. P. Mahalik, J. W. Dugger, S. W. Sides, B. G. Sumpter, V. Lauter and R. Kumar, Interpreting neutron reflectivity profiles of diblock copolymer nanocomposite thin films using hybrid particle-field simulations, Macromolecules, 2018, 51(8), 3116; J. P. Mahalik, W. Li, A. T. Savici, S. Hahn, H. Lauter, H. Ambaye, B. G. Sumpter, V. Lauter and R. Kumar, Dispersity-driven stabilization of coexisting morphologies in asymmetric diblock copolymer thin films, Macromolecules, 2021, 54(1), 450). However, extracting Flory-Huggins χ parameters characterizing monomer-monomer, monomer-substrate, and monomer-air interactions has been labor-intensive and prone to errors, requiring the use of alternative methods for practical purposes. In this work, we have developed such an alternative method by employing a multi-layer perceptron, an autoencoder, and a variational autoencoder. These neural networks are used to extract interaction parameters not only from neutron scattering length density profiles constructed using self-consistent field theory-based simulations, but also from a noisy ad hoc model constructed previously. In particular, the variational autoencoder is shown to be the most promising tool when it comes to the reconstruction and extraction of parameters from an ad hoc neutron scattering length density profile of a thin film containing a symmetric di-block copolymer (poly(deuterated styrene-b-n-butyl methacrylate)). This work paves the way for automated analysis of specular neutron reflectivities from thin films of copolymers using machine learning tools.

Robust Copper-Based Nanosponge Architecture Decorated by Ruthenium with Enhanced Electrocatalytic Performance for Ambient Nitrogen Reduction to Ammonia.

Electrochemical conversion of nitrogen to green ammonia is an attractive alternative to the Haber-Bosch process. However, it is currently bottlenecked by the lack of highly efficient electrocatalysts to drive the sluggish nitrogen reduction reaction (N2RR). Herein, we strategically design a cost-effective bimetallic Ru-Cu mixture catalyst in a nanosponge (NS) architecture via a rapid and facile method. The porous NS mixture catalysts exhibit a large electrochemical active surface area and enhanced specific activity arising from the charge redistribution for improved activation and adsorption of the activated nitrogen species. Benefiting from the synergistic effect of the Cu constituent on morphology decoration and thermodynamic suppression of the competing hydrogen evolution reaction, the optimized Ru0.15Cu0.85 NS catalyst presents an impressive N2RR performance with an ammonia yield rate of 26.25 µg h-1 mgcat.-1 (corresponding to 10.5 µg h-1 cm-2) and Faradic efficiency of 4.39% as well as superior stability in alkaline medium, which was superior to that of monometallic Ru and Cu nanostructures. Additionally, this work develops a new bimetallic combination of Ru and Cu, which promotes the strategy to design efficient electrocatalysts for electrochemical ammonia production under ambient conditions.

The Atomic Drill Bit: Precision Controlled Atomic Fabrication of 2D Materials.

The ability to deterministically fabricate nanoscale architectures with atomic precision is the central goal of nanotechnology, whereby highly localized changes in the atomic structure can be exploited to control device properties at their fundamental physical limit. Here, an automated, feedback-controlled atomic fabrication method is reported and the formation of 1D-2D heterostructures in MoS2 is demonstrated through selective transformations along specific crystallographic orientations. The atomic-scale probe of an aberration-corrected scanning transmission electron microscope (STEM) is used, and the shape and symmetry of the scan pathway relative to the sample orientation are controlled. The focused and shaped electron beam is used to reliably create Mo6 S6 nanowire (MoS-NW) terminated metallic-semiconductor 1D-2D edge structures within a pristine MoS2 monolayer with atomic precision. From these results, it is found that a triangular beam path aligned along the zig-zag sulfur terminated (ZZS) direction forms stable MoS-NW edge structures with the highest degree of fidelity without resulting in disordering of the surrounding MoS2 monolayer. Density functional theory (DFT) calculations and ab initio molecular dynamic simulations (AIMD) are used to calculate the energetic barriers for the most stable atomic edge structures and atomic transformation pathways. These discoveries provide an automated method to improve understanding of atomic-scale transformations while opening a pathway toward more precise atomic-scale engineering of materials.

Understanding Heterogeneities in Quantum Materials.

Quantum materials are usually heterogeneous, with structural defects, impurities, surfaces, edges, interfaces, and disorder. These heterogeneities are sometimes viewed as liabilities within conventional systems; however, their electronic and magnetic structures often define and affect the quantum phenomena such as coherence, interaction, entanglement, and topological effects in the host system. Therefore, a critical need is to understand the roles of heterogeneities in order to endow materials with new quantum functions for energy and quantum information science applications. In this article, several representative examples are reviewed on the recent progress in connecting the heterogeneities to the quantum behaviors of real materials. Specifically, three intertwined topic areas are assessed: i) Reveal the structural, electronic, magnetic, vibrational, and optical degrees of freedom of heterogeneities. ii) Understand the effect of heterogeneities on the behaviors of quantum states in host material systems. iii) Control heterogeneities for new quantum functions. This progress is achieved by establishing the atomistic-level structure-property relationships associated with heterogeneities in quantum materials. The understanding of the interactions between electronic, magnetic, photonic, and vibrational states of heterogeneities enables the design of new quantum materials, including topological matter and quantum light emitters based on heterogenous 2D materials.

Quantum theory of electronic excitation and sputtering by transmission electron microscopy.

Many computational models have been developed to predict the rates of atomic displacements in two-dimensional (2D) materials under electron beam irradiation. However, these models often drastically underestimate the displacement rates in 2D insulators, in which beam-induced electronic excitations can reduce the binding energies of the irradiated atoms. This bond softening leads to a qualitative disagreement between theory and experiment, in that substantial sputtering is experimentally observed at beam energies deemed far too small to drive atomic dislocation by many current models. To address these theoretical shortcomings, this paper develops a first-principles method to calculate the probability of beam-induced electronic excitations by coupling quantum electrodynamics (QED) scattering amplitudes to density functional theory (DFT) single-particle orbitals. The presented theory then explicitly considers the effect of these electronic excitations on the sputtering cross section. Applying this method to 2D hexagonal BN and MoS2 significantly increases their calculated sputtering cross sections and correctly yields appreciable sputtering rates at beam energies previously predicted to leave the crystals intact. The proposed QED-DFT approach can be easily extended to describe a rich variety of beam-driven phenomena in any crystalline material.

Phase Transition Dynamics in a Complex Oxide Heterostructure.

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO_{x} and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. The experimental and theoretical methods described here are broadly applicable to in situ measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

Extracting Inelastic Scattering Cross Sections for Finite and Aperiodic Materials from Electronic Dynamics Simulations.

Explicit time-dependent electronic structure theory methods are increasingly prevalent in the areas of condensed matter physics and quantum chemistry, with the broad-band optical absorptivity of molecular and small condensed-phase systems nowadays routinely studied with such approaches. In this paper, it is demonstrated that electronic dynamics simulations can similarly be employed to study cross sections for the scattering-induced electronic excitations probed in nonresonant inelastic X-ray scattering and momentum-resolved electron energy loss spectroscopies. A method is put forth for evaluating the electronic dynamic structure factor, which involves the application of a momentum boost-type perturbation and transformation of the resulting reciprocal space density fluctuations into the frequency domain. Good agreement is first demonstrated between the dynamic structure factor extracted from these electronic dynamics simulations and the corresponding transition matrix elements from linear response theory. The method is then applied to some extended (quasi)one-dimensional systems, for which the wave vector becomes a good quantum number in the thermodynamic limit. Finally, the dispersion of many-body excitations in a series of hydrogen-terminated graphene flakes (and twisted bilayers thereof) is investigated to highlight the utility of the presented approach for capturing morphology-dependent effects in the inelastic scattering cross sections of nanostructured and/or noncrystalline materials.

Quantum Spin Hall Edge States and Interlayer Coupling in Twisted Bilayer WTe2.

The quantum spin Hall (QSH) effect, characterized by topologically protected spin-polarized edge states, was recently demonstrated in monolayers of the transition metal dichalcogenide (TMD) WTe2. However, the robustness of this topological protection remains largely unexplored in van der Waals heterostructures containing one or more layers of a QSH insulator. In this work, we use scanning tunneling microscopy and spectroscopy (STM/STS) to explore the topological nature of twisted bilayer (tBL) WTe2. At the tBL edges, we observe the characteristic spectroscopic signatures of the QSH edge states. For small twist angles, a rectangular moiré pattern develops, which results in local modifications of the band structure. Using first-principles calculations, we quantify the interactions in tBL WTe2 and its topological edge states as a function of interlayer distance and conclude that it is possible to engineer the topology of WTe2 bilayers via the twist angle as well as interlayer interactions.

Reversible Hydrogen-Induced Phase Transformations in La0.7Sr0.3MnO3 Thin Films Characterized by In Situ Neutron Reflectometry.

We report on the mechanism for hydrogen-induced topotactic phase transitions in perovskite (PV) oxides using La0.7Sr0.3MnO3 as a prototypical example. Hydrogenation starts with lattice expansion confirmed by X-ray diffraction (XRD). The strain- and oxygen-vacancy-mediated electron-phonon coupling in turn produces electronic structure changes that manifest through the appearance of a metal insulator transition accompanied by a sharp increase in resistivity. The ordering of initially randomly distributed oxygen vacancies produces a PV to brownmillerite phase (La0.7Sr0.3MnO2.5) transition. This phase transformation proceeds by the intercalation of oxygen vacancy planes confirmed by in situ XRD and neutron reflectometry (NR) measurements. Despite the prevailing picture that hydrogenation occurs by reaction with lattice oxygen, NR results are not consistent with deuterium (hydrogen) presence in the La0.7Sr0.3MnO3 lattice at steady state. The film can reach a highly oxygen-deficient La0.7Sr0.3MnO2.1 metastable state that is reversible to the as-grown composition simply by annealing in air. Theoretical calculations confirm that hydrogenation-induced oxygen vacancy formation is energetically favorable in La0.7Sr0.3MnO3. The hydrogenation-driven changes of the oxygen sublattice periodicity and the electrical and magnetic properties similar to interface effects induced by oxygen-deficient cap layers persist despite hydrogen not being present in the lattice.

A combined first principles study of the structural, magnetic, and phonon properties of monolayer CrI3.

The first magnetic 2D material discovered, monolayer (ML) CrI3, is particularly fascinating due to its ground state ferromagnetism. However, because ML materials are difficult to probe experimentally, much remains unresolved about ML CrI3's structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin-phonon and spin-lattice coupling of ML CrI3. We exploit a recently developed surrogate Hessian DMC line search technique to determine CrI3's ML geometry with DMC accuracy, yielding lattice parameters in good agreement with recently published STM measurements-an accomplishment given the ∼10% variability in previous DFT-derived estimates depending upon the functional. Strikingly, we find that previous DFT predictions of ML CrI3's magnetic spin moments are correct on average across a unit cell but miss critical local spatial fluctuations in the spin density revealed by more accurate DMC. DMC predicts that magnetic moments in ML CrI3 are 3.62 µB per chromium and -0.145 µB per iodine, both larger than previous DFT predictions. The large disparate moments together with the large spin-orbit coupling of CrI3's I-p orbital suggest a ligand superexchange-dominated magnetic anisotropy in ML CrI3, corroborating recent observations of magnons in its 2D limit. We also find that ML CrI3 exhibits a substantial spin-phonon coupling of ∼3.32 cm-1. Our work, thus, establishes many of ML CrI3's key properties, while also continuing to demonstrate the pivotal role that DMC can assume in the study of magnetic and other 2D materials.

Oxygen Vacancy Injection as a Pathway to Enhancing Electromechanical Response in Ferroelectrics.

Since their discovery in late 1940s, perovskite ferroelectric materials have become one of the central objects of condensed matter physics and materials science due to the broad spectrum of functional behaviors they exhibit, including electro-optical phenomena and strong electromechanical coupling. In such disordered materials, the static properties of defects such as oxygen vacancies are well explored but the dynamic effects are less understood. In this work, the first observation of enhanced electromechanical response in BaTiO3 thin films is reported driven via dynamic local oxygen vacancy control in piezoresponse force microscopy (PFM). A persistence in peizoelectricity past the bulk Curie temperature and an enhanced electromechanical response due to a created internal electric field that further enhances the intrinsic electrostriction are explicitly demonstrated. The findings are supported by a series of temperature dependent band excitation PFM in ultrahigh vacuum and a combination of modeling techniques including finite element modeling, reactive force field, and density functional theory. This study shows the pivotal role that dynamics of vacancies in complex oxides can play in determining functional properties and thus provides a new route toward- achieving enhanced ferroic response with higher functional temperature windows in ferroelectrics and other ferroic materials.

Inflammatory bowel diseases in Tamil Nadu: A survey of demographics, clinical profile, and practices.

BACKGROUND: Inflammatory bowel disease (IBD) is increasingly diagnosed in South Asia. This survey by the Tamil Nadu Chapter of the Indian Society of Gastroenterology (TNISG) documents the demography, clinical profile, and therapeutic practices related to IBD in Tamil Nadu. METHODS: TNISG members from 32 institutions completed an online cross-sectional questionnaire on IBD patients from March 2020 to January 2021. RESULTS: Of 1295 adult IBD patients, 654 had Crohn's disease (CD), 499 ulcerative colitis (UC), and 42 IBD-unclassified (IBD-U). CD and UC showed a unimodal age distribution. A total of 55% were graduates or postgraduates. A positive family history was noted in 30, other risk factors were uncommon. In CD, the pattern of involvement was ileocolonic (42.8%), ileal (34.7%), colonic (18.9%), and upper gastrointestinal (3.5%); while in UC, disease was characterized as extensive (44.9%), left-sided (41.7%), or proctitis (13.4%). Perineal disease, perianal fistulae, and bowel obstruction were noted in 4.3, 14.0, and 23.5%, respectively, of CD. The most widely used drugs were mesalamine, azathioprine, and corticosteroids. Surgery was undertaken in 141 patients with CD and 23 patients with UC. Of the 138 patients with pediatric IBD (≤16 years), 23 were characterized as very early onset IBD (VEO-IBD), 27 as early-onset, and 88 as adolescent IBD. VEO-IBD were more likely to have a positive family history of IBD and were more likely to have perineal disease and to have the IBD-U phenotype. Among pediatric IBD patients, corticosteroids, mesalamine, and azathioprine were the most commonly used medications, while 25 pediatric patients received biologics. CONCLUSION: This study provides important information on demography, clinical profile, and treatment practices of IBD in India.