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At least 703 records · Page 39

Local magnetic moments due to loop currents in metals

We present Hartree-Fock calculations on a simple model to obtain the conditions of formation of local magnetic moments due to loop currents $L$ $o$ and spin-loop currents $L$ $s$ and compare them to the conditions of formation of local spin moments $M$ which were given long ago in a similar approximation by Anderson. A model with three degenerate orbitals sitting on an equilateral triangle, with on-site and nearest-neighbor repulsions $U$ and $V$, respectively, and intersite kinetic energy, hybridizing with conduction electrons with a parameter $Δ$ is investigated. $L$ $o$ and $L$ $s$ are promoted by large $V$/$Δ$ and their magnitude is relatively unaffected by $U$/$Δ$. Spin-magnetic moments $M$ promoted by large $U$/$Δ$ on the other hand are adversely affected by $V$/$Δ$. In this model, $L$ $o$ for $V$ multiplied by the number of neighbors is approximately the same as the $M$ promoted by $U$ in Anderson’s local model for $M$. $L$ $o$ and $L$ $s$ are degenerate if exchange interactions and Hund’s rule are neglected but $L$ $o$ is favored when they are included. Many of the qualitative results are visible in an expression for the Hartree-Fock ground state energy derived as a function of small $L$ $o$ , $L$ $s$ , and $M$. Numerical minimization of the Hartree-Fock energy is presented for larger values. Additionally, we also briefly discuss the connection and differences of the interaction-generated orbital currents and spin currents discussed here and generalized to a lattice with the topological states in metals and semiconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Asymmetric side-chain engineering in semiconducting polymers: a platform for greener processing and post-functionalization of organic electronics

Organic semiconducting polymers are a powerful platform for the design of next-generation technologies due to their excellent optoelectronic properties and solution processability, allowing access to low-cost and scalable manufacturing techniques such as spin-coating, slot-die coating and roll-to-roll printing. However, their extended π-conjugation results in low solubility, requiring the use of toxic halogenated solvents to generate thin films and devices. Furthermore, accessible post-functionalization of semiconductors toward the development of multifunctional devices and sensors remains a challenge due to limited solid-state chemistry for alkyl side chains. In this work, an asymmetric side-chain engineering approach was used to introduce terminal hydroxyl moieties alongside traditional solubilizing branched alkyl chains into an isoindigo-based polymer. The hydroxyl moieties led to significantly improved processability in alcohol-based solvents without sacrificing electronic performance in thin film organic field-effect transistors. Solid state morphologies of the thin films processed from both alcohol-based and traditional halogenated solvents were further characterized using atomic force microscopy and grazing incidence wide angle X-ray scattering. Additionally, Cryo-EM was utilized in order to characterize the role of asymmetric side-chain functionality in solution state aggregation. The versatility of this design was further probed using fluorescein isothiocyanate to directly functionalize the asymmetric polymer in thin film. Furthermore, this facile solid-state post-functionalization further demonstrates asymmetric side-chain engineering to be a viable approach toward the development of sustainably manufactured multifunctional electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Majorana bound states in a d -wave superconductor planar Josephson junction

We study phase-controlled planar Josephson junctions comprising a two-dimensional electron gas with strong spin-orbit coupling and d-wave superconductors, which have an advantage of a high critical temperature. We show that a region between the two superconductors can be tuned into a topological state by the in-plane Zeeman field, and can host Majorana bound states. The phase diagram as a function of the Zeeman field, chemical potential, and the phase difference between superconductors exhibits the appearance of Majorana bound states for a wide range of parameters. We further investigate the behavior of the topological gap and its dependence on the type of d-wave pairing, i.e., d, d+is, or d+id', and note the difficulties that can arise due to the presence of gapless excitations in pure d-wave superconductors. On the other hand, the planar Josephson junctions based on superconductors with d+is and d+id' pairings can potentially lead to realizations of Majorana bound states. Furthermore, our proposal can be realized in cuprate superconductors, e.g., in a twisted bilayer, combined with the layered semiconductor Bi 2 O 2 Se.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solid‐state nuclear magnetic resonance of spin‐9/2 nuclei 115 In and 209 Bi in functional inorganic complex oxides

Abstract Indium and bismuth are technologically important elements, in particular as oxides for optoelectronic applications. 115 In and 209 Bi are both I = 9/2 nuclei with high natural abundances and moderately high frequencies but large nuclear electric quadrupole moments. Leveraging the quadrupolar interaction as a measure of local symmetry and polyhedral distortions for these nuclei could provide powerful insights on a range of applied materials. However, the absence of reported nuclear magnetic resonance (NMR) parameters on these nuclei, particularly in oxides, hinders their use by the broader materials community. In this contribution, solid‐state 115 In and 209 Bi NMR of three recently discovered quaternary bismuth or indium oxides are reported, supported by density functional theory calculations, numerical simulations, diffraction and additional multinuclear ( 27 Al, 69,71 Ga, and 121 Sb) solid‐state NMR measurements. The compounds LiIn 2 SbO 6 , BiAlTeO 6 , and BiGaTeO 6 are measured without special equipment at 9.4 T, demonstrating that wideline techniques such as the QCPMG pulse sequence and frequency‐stepped acquisition can enable straightforward extraction of quadrupolar tensor information in I = 9/2 115 In and 209 Bi even in sites with large quadrupolar coupling constants. Relationships are described between the NMR observables and local site symmetry. These are amongst the first reports of the NMR parameters of 115 In, 121 Sb, and 209 Bi in oxides.

Griffith, Kent J.↗

Aqueous solvation of the chloride ion revisited with density functional theory: impact of correlation and exchange approximations

The specificity of aqueous halide solvation is fundamental to a wide range of bulk and interfacial phenomena spanning from biology to materials science. Halide polarizability is thought to drive the ion specificity, and if so, it is essential to have an accurate description of the electronic properties of halide ions in water. To this end, the solvation of the chloride anion, Cl - has been reinvestigated with state-of-the-art density functional theory. Specifically, the PBE-D3, PBE0-D3, and SCAN functionals have been employed to probe the impact of correlation and exchange approximations. Anticipating the findings, adding exact exchange improves the electronic structure, but simultaneously significantly reduces the Cl - polarizability, resulting in an over-structured Cl–O radial distribution function (RDF) and longer water H-bond lifetimes to Cl - . SCAN does not yield as much improvement in the energetics of Cl - relative to bulk water, but does result in a smaller reduction of the polarizability and thus a less structured Cl–O RDF, which agrees better with experiment. Special consideration is therefore warranted in assessing the impact of exchange on the energy, charge density, and the charge density response when designing and testing hybrid functionals for aqueous halide solvation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bending as a control knob for the electronic and optical properties of phosphorene nanoribbons

We have assessed mechanical bending as a powerful controlling tool for the electronic structure and optical properties of phosphorene nanoribbons. We use state-of-the-art density functional approximations in our work. The overall performance of the recently developed meta-generalized gradient approximation (meta-GGA) mTASK [Phys. Rev. Materials 5, 063803 (2021)] functional establishes the method as a useful alternative to the screened hybrid HSE06 for better band gaps of phosphorene nanoribbons. We present a detailed analysis to interpret the optical absorption of bent phosphorene nanoribbons using the GW-Bethe-Salpeter approximation. Finally, we demonstrate the important role of the unoccupied in-gap state and conclude that this in-gap state in armchair nanoribbons introduced by bending can significantly affect the properties of low-energy excitons and add some useful opportunities for applications in optoelectronic devices.

36 MATERIALS SCIENCE↗

Linearized Pair-Density Functional Theory for Vertical Excitation Energies

Multiconfiguration pair-density functional theory (MC-PDFT) is a computationally efficient method that computes the energies of electronic states in a state specific or state average framework via an on-top functional. However, MC-PDFT does not include state interaction among these states since the final energies do not come from the diagonalization of an effective model-space Hamiltonian. Recently, multistate extensions such as linearized PDFT (L-PDFT) have been developed to accurately model the potentials near conical intersections and avoided crossings. However, there has not been any systematic study evaluating their performance for predicting vertical excitations at the equilibrium geometry of a molecule, when the excited states are generally well separated. In this paper, we report the performance of L-PDFT on the extensive QUESTDB data set of vertical excitations using a database of automatically selected active spaces. We show that L-PDFT performs well on all these excitations and successfully reproduces the performance of MC-PDFT. These results further demonstrate the potential of L-PDFT, as its scaling is constant with the number of states included in the state-average manifold, whereas MC-PDFT scales linearly in this regard.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Lifetimes of Photoinduced Deligation in a Metal–Organic Framework via Linker Functionalization

Recently photoinduced dynamic ligation in a metal–organic frameworks (MOFs) was reported, where a long-lived charge-transfer excited state (ca. 30 μs) featuring partial dissociation between the carboxylate linker and metal-based node was probed by time-resolved infrared (TRIR) spectroscopy. The study offers a new mechanistic perspective to evaluate the potential contribution from the excited state molecular configuration to the performance of MOF photocatalysts. In this work, by employing MIL-101(Fe) as the study platform, we have further explored the influence of intramolecular interactions on the stability of relevant excited states and demonstrated the effective tuning of their lifetimes through the incorporation of different functional groups into the system. The correlations between the varied excited state lifetimes and coordination configurations with specific functional groups (−NH 2 or −NO 2 ) was inferred from the analyses of infrared spectroscopic data and theoretical calculations, revealing the essential role of the intramolecular interactions (i.e., between the added functional groups and the carboxylate group) in the modulation of system energetics. Overall, the work presents a pathway to tune the excited state dynamics and expands the knowledge regarding the photoinduced dynamic ligation in carboxylate-based MOFs.

excited states↗

Proton-Coupled Electron Transfer in a Ruthenium(II) Bipyrimidine Complex in Its Ground and Excited Electronic States

In this work, proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH 2 )(PF 6 ) 2 ] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH 2 in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV–vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes $τ_1$ = 4 ps and $τ_2$ = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 ($τ_1$) and 1.61 ($τ_2$) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the 3 MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the 3 MLCT state. The hydrogen-bonded state 3 MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the 3 MLCT state to the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput determination of Hubbard $U$ and Hund $J$ values for transition metal oxides via the linear response formalism

DFT+U provides a convenient, cost-effective correction for the self-interaction error (SIE) that arises when describing correlated electronic states using conventional approximate density functional theory (DFT). The success of a DFT+U(+J) calculation hinges on the accurate determination of its Hubbard U and Hund J parameters, and the linear response (LR) methodology has proven to be computationally effective and accurate for calculating these parameters. This study provides a high-throughput computational analysis of the U and J values for transition metal d-electron states in a representative set of over 1000 magnetic transition metal oxides (TMOs), providing a frame of reference for researchers who use DFT+U to study transition metal oxides. In order to perform this high-throughput study, an ATOMATE workflow is developed for calculating U and J values automatically on massively parallel supercomputing architectures. Here, to demonstrate an application of this workflow, the spin-canting magnetic structure and unit cell parameters of the multiferroic olivine LiNiPO4 are calculated using the computed Hubbard U and Hund J values for Ni-d and O-p states, and are compared with experiment. Both the Ni-d U and J corrections have a strong effect on the Ni-moment canting angle. Additionally, including a O-pU value results in a significantly improved agreement between the computed lattice parameters and experiment

36 MATERIALS SCIENCE↗

Engineering Functionalized 2D Metal-Organic Frameworks Nanosheets with Fast Li + Conduction for Advanced Solid Li Batteries

Solid-state batteries can ensure high energy density and safety in lithium metal batteries, while polymer electrolytes are plagued by slow ion kinetics and low selective transport of Li + . Metal-organic frameworks (MOFs) are proposed as emerging fillers for solid-state poly(ethylene oxide)(PEO) electrolytes, however, developing functionalized MOFs and understanding their roles on ion transfer has proven challenging. Herein, combining computational and experimental results, the functional group regulation in MOFs can effectively change surficial charge distribution and limit anion movement is revealed, providing a potential solution to these issues. Specifically, functionalized 2D MOF sheets are designed through molecular engineering to construct high-performance composite electrolytes, where the electron-donating effect of substituents in 2D-MOFs effectively limits the movement of ClO 4 - and promotes mechanical properties and ion migration numbers (0.36 up to 0.64) of PEO. As a result, Li/Li cells with composite electrolyte exhibit superior cyclability for 1000 h at a current density of 0.2 mA cm -2 . Meanwhile, the solid LiFePO 4 /Li battery delivers highly reversible capacities of 148.8 mAh g -1 after 200 cycles. In conclusion, these findings highlight a new approach for anion confinement through the use of functional group electronic effects, leading to enhanced ionic conductivity, and a feasible direction for high-performance solid-state batteries.

25 ENERGY STORAGE↗

Time correlations from steady-state expectation values

Recovering properties of correlation functions is typically challenging. On one hand, experimentally, it requires measurements with a temporal resolution finer than the system's dynamics. On the other hand, analytical or numerical analysis requires solving the system evolution. Here, we use recent results of quantum metrology with continuous measurements to derive general lower bounds on the relaxation and second-order correlation times that are both easy to calculate and measure. These bounds are based solely on steady-state expectation values and their derivatives with respect to a control parameter, and can be readily extended to the autocorrelation of arbitrary observables. We validate our method on two examples of critical quantum systems: a critical driven-dissipative resonator, where the bound matches analytical results for the dynamics, and the infinite-range Ising model, where only the steady state is solvable and thus the bound provides information beyond the reach of existing analytical approaches. Our results can be applied to experimentally characterize ultrafast systems, and to theoretically analyze many-body models with dynamics that are analytically or numerically hard.

Górecki, Wojciech [INFN, Pavia]↗

Time correlations from steady-state expectation values

Recovering properties of correlation functions is typically challenging. On one hand, experimentally, it requires measurements with a temporal resolution finer than the system's dynamics. On the other hand, analytical or numerical analysis requires solving the system evolution. Here, we use recent results of quantum metrology with continuous measurements to derive general lower bounds on the relaxation and second-order correlation times that are both easy to calculate and measure. These bounds are based solely on steady-state expectation values and their derivatives with respect to a control parameter, and can be readily extended to the autocorrelation of arbitrary observables. We validate our method on two examples of critical quantum systems: a critical driven-dissipative resonator, where the bound matches analytical results for the dynamics, and the infinite-range Ising model, where only the steady state is solvable and thus the bound provides information beyond the reach of existing analytical approaches. Our results can be applied to experimentally characterize ultrafast systems, and to theoretically analyze many-body models with dynamics that are analytically or numerically hard.

Górecki, Wojciech [INFN, Pavia]↗

Giant gravitons, Harish-Chandra integrals, and BPS states in symplectic and orthogonal $\mathcal{N}$ = 4 SYM

We find generating functions for half BPS correlators in $\mathcal{N}$ = 4 SYM theories with gauge groups Sp(2N), SO(2N + 1), and SO(2N) by computing the norms of a class of BPS coherent states. These coherent states are built from operators involving Harish-Chandra integrals. Such operators have an interpretation as localized giant gravitons in the bulk of anti-de-Sitter space. This extends the analysis of [1] to Sp(2N), SO(2N + 1), and SO(2N) gauge theories. We show that we may use ordinary Schur functions as a basis for the sector of states with no cross-caps in these theories. This is consistent with the construction of these theories as orientifold projections of an SU(2N) theory. We make note of some relations between the symmetric functions that appear in the expansion of these coherent states and symplectic Schur functions. We also comment on some connections to Schubert calculus and Gromov-Witten invariants, which suggest that the Harish-Chandra integral may be extended to such problems.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Time Correlations from Steady-State Expectation Values

Recovering properties of correlation functions is typically challenging. On the one hand, experimentally, it requires measurements with a temporal resolution finer than the system’s dynamics. On the other hand, analytical or numerical analysis requires solving the system evolution. Here, we use recent results of quantum metrology with continuous measurements to derive general lower bounds on the relaxation and second-order correlation times that are both easy to calculate and measure. These bounds are based solely on steady-state expectation values and their derivatives with respect to a system parameter, and can be readily extended to the autocorrelation of arbitrary observables. We validate our method on two examples of critical quantum systems: a critical driven-dissipative resonator, where the bound matches analytical results for the dynamics, and the infinite-range Ising model, where only the steady state is solvable, and thus the bound provides information beyond the reach of existing analytical approaches. Our results can be applied to the experimental characterization of ultrafast systems and to the theoretical analysis of many-body models whose dynamics are hard to compute.

Górecki, Wojciech [INFN, Pavia] (ORCID:00000001991↗

Design principles and physical properties of two-dimensional heterostructured borides

Principles of design to create dynamically stable transition metal-, lanthanide-, and actinide-based low-dimensional borides are presented. A charge transfer analysis of donor metal atoms to electron deficient honeycombed B lattices allows to predict complex covalent heterostructures hosting Dirac states. The applicable guidelines are supported with the analysis of phonon spectra computed with first-principles calculations to demonstrate the physical stability of nanometer-thick heterostructures. Similar or dissimilar layered borides can be stacked on top of each other in a layer-by-layer fashion creating compounds that can be fundamentally different from the individual layers, opening a rich playground to explore novel physical properties and new materials. Functionalities such as multiple Dirac states, highly dispersive electronic bands, and decoupled acoustic-optical phonon branches are studied. The combination of appealing electronic properties and physical realization makes of predicted layered borides promising materials to integrate a new generation of two-dimensional materials.

2-dimensional systems↗

A Sustainable Multi-Dimensional Printable Material

Polymeric materials are usually tailored for specific functionality. A single polymer exhibiting multiple simultaneous functionalities often requires intricate molecular architecture, which is difficult to manufacture at scale because of its complex synthesis routes. In this work, a facile, partly renewable composition—prepared via reactive melt processing—that induces tunable functionalities such as 3D printability, shape recovery, and self-healing while exhibiting satisfactory mechanical properties is reported. The system with a hydrogen-bonded 3D network consists of thermally reversible nano-scale agglomerates of sustainable, rigid phenolic oligomers and crystallizable flexible polymer. Local molecular mobility and temperature-dependent relaxation and recovery of the non-equilibrium networked states enable exploiting these simultaneous functionalities. Transitions involving solidification and structure stabilization at ambient temperature spanning several hours after preheating only at 70 °C directly contrast typical thermoplastic or thermoplastic elastomer behaviors. Results from this study can inform the design of future rheology modifiers and materials for soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shining light on nanoscale ‘vine-on-stick’ eutectic structures in the Al-Ce-Ni system

Multiphase eutectics often comprise entangled solid phases with nanoscale periodicity, making it difficult to unravel their 3D connectivity using conventional 2D techniques. Among such systems, the three-phase eutectic Al-Al 11 Ce 3 -Al 3 Ni stands out for its ultrafine (∼100 nm) interphase spacing and promising creep resistance, yet its microstructure remains relatively unexplored despite its potential for high-temperature applications. Here, we use scanning hard X-ray microscopy with an unprecedented ∼10 nm pixel size to resolve its 3D morphology. Reconstructions reveal a novel “vine-on-stick” motif, wherein Al 11 Ce 3 wraps around Al 3 Ni pillars. Analysis of phase tortuosities confirms that Al 11 Ce 3 exhibits more convoluted morphologies than Al 3 Ni. No orientation relationship was observed between the two intermetallics, suggesting that growth is controlled by local solute gradients rather than epitaxy. Fragmentation of intermetallics along their longitudinal axis suggests a Rayleigh-type breakup mechanism in solid state. The “vine-on-stick” pattern may generalize to other alloy systems with variable interfacial anisotropies and low mutual solubilities.

36 MATERIALS SCIENCE↗