Spin Interactions Research Articles

Toward Accelerating Discovery via Physics-Driven and Interactive Multifidelity Bayesian Optimization

Abstract Both computational and experimental material discovery bring forth the challenge of exploring multidimensional and often nondifferentiable parameter spaces, such as phase diagrams of Hamiltonians with multiple interactions, composition spaces of combinatorial libraries, processing spaces, and molecular embedding spaces. Often these systems are expensive or time consuming to evaluate a single instance, and hence classical approaches based on exhaustive grid or random search are too data intensive. This resulted in strong interest toward active learning methods such as Bayesian optimization (BO) where the adaptive exploration occurs based on human learning (discovery) objective. However, classical BO is based on a predefined optimization target, and policies balancing exploration and exploitation are purely data driven. In practical settings, the domain expert can pose prior knowledge of the system in the form of partially known physics laws and exploration policies often vary during the experiment. Here, we propose an interactive workflow building on multifidelity BO (MFBO), starting with classical (data-driven) MFBO, then expand to a proposed structured (physics-driven) structured MFBO (sMFBO), and finally extend it to allow human-in-the-loop interactive interactive MFBO (iMFBO) workflows for adaptive and domain expert aligned exploration. These approaches are demonstrated over highly nonsmooth multifidelity simulation data generated from an Ising model, considering spin–spin interaction as parameter space, lattice sizes as fidelity spaces, and the objective as maximizing heat capacity. Detailed analysis and comparison show the impact of physics knowledge injection and real-time human decisions for improved exploration with increased alignment to ground truth. The associated notebooks allow to reproduce the reported analyses and apply them to other systems.2

Selective Methods Promote Protein Solid-State NMR.

Solid-state nuclear magnetic resonance (ssNMR) is indispensable for studying the structures, dynamics, and interactions of insoluble proteins in native or native-like environments. While ssNMR includes numerous nonselective techniques for general analysis, it also provides various selective methods that allow for the extraction of precise details about proteins. This perspective highlights three key aspects of selective methods: selective signals of protein segments, selective recoupling, and site-specific insights into proteins. These methods leverage protein topology, labeling strategies, and the tailored manipulation of spin interactions through radio frequency (RF) pulses, significantly promoting the field of protein ssNMR. With ongoing advancements in higher magnetic fields and faster magic angle spinning (MAS), there remains an ongoing need to enhance the selectivity and efficiency of selective ssNMR methods, facilitating deeper atomic-level insights into complex biological systems.

New Constraints on Axion-Mediated Spin Interactions Using Magnetic Amplification

New Constraints on Axion-Mediated Spin Interactions Using Magnetic Amplification

An instructional lab apparatus for quantum experiments with single nitrogen-vacancy centers in diamond

Hands-on experimental experience with quantum systems in the undergraduate physics curriculum provides students with a deeper understanding of quantum physics and equips them for the fast-growing quantum science industry. Here, we present an experimental apparatus for performing quantum experiments with single nitrogen-vacancy (NV) centers in diamond. This apparatus is capable of basic experiments such as single-qubit initialization, rotation, and measurement, as well as more advanced experiments investigating electron–nuclear spin interactions. We describe the basic physics of the NV center and give examples of potential experiments that can be performed with this apparatus. We also discuss the options and inherent trade-offs associated with the choice of diamond samples and hardware. The apparatus described here enables students to write their own experimental control and data analysis software from scratch, all within a single semester of a typical lab course, as well as to inspect the optical components and inner workings of the apparatus. We hope that this work can serve as a standalone resource for any institution that would like to integrate a quantum instructional lab into its undergraduate physics and engineering curriculum.

Structural Manipulation of Spin Excitations in a Molecular Junction.

Single metallocene molecules act as sensitive spin detectors when decorating the probe of a scanning tunneling microscope (STM). However, the impact of the atomic-scale electrode details on the molecular spin state has remained elusive to date. Here, a nickelocene (Nc) STM junction is manipulated in an atomwise manner showing clearly the dependence of the spin excitation spectrum on the anchoring of Nc to Cu(111), a Cu monomer, and trimer. Moreover, while the spin state of the same Nc tip is a triplet with tunable spin excitation energies upon contacting the surface, it transitions to a Kondo-screened doublet on a Cu atom. Notably, the nontrivial magnetic exchange interaction of the molecular spin with the electron continuum of the substrate determines the spectral line shape of the spin excitations.

“Nutation” of electron spins in biradicals

In this work, the nutation of the spins of unpaired electrons in the nitroxide biradical of bis‑methano[60]fullerene was experimentally studied. Nutation frequencies were found in a wide range of microwave field power. To interpret the obtained results, numerical calculations of the nutation of biradicals were carried out for a set of parameters of the spin–spin interaction of a pair of unpaired electrons and for different values of the Rabi frequency of the microwave field. At comparing numerical results with experimental data, we also used the results of analytical calculations of nutation for some model situations. As a result of the analysis of experimental data on nutation, an estimate of the exchange and dipole–dipole interactions for the studied biradical was obtained. They are consistent with the results obtained from analysis of the shape of the EPR spectrum for a given biradical.

Thermoelectric Performance in Triplet‐Ground‐State Polymer Intrinsically Boosted by Enhanced Proquinoidal Characteristic

AbstractOver the past decade, polymer thermoelectric materials featuring flexibility, lightness, and bio‐friendliness have been paid increasing attention as promising candidates for waste heat recovery and energy generation. For a long time, the dominant approach to optimizing the thermoelectric performance of most organic materials is chemical doping, which, however, is not always ideal for practical applications due to its tendency to involve intricate processing procedure and trigger material and device instability. Currently, the pursuit of single‐component neutral thermoelectric materials without exogenous doping presents a compelling alternative. In this work, we designed and synthesized a high‐spin polymer material, PBBT‐TT, by simultaneously employing thieno[3,4‐b]thiophene (TbT) and benzo[1,2‐c : 4,5‐c′]bis[1,2,5]thiadiazole (BBT) units with pronounced proquinoidal characteristics, its analogue, PBBT‐T to demonstrate the effect of the TbT unit was also synthesized. The results indicate that because of the enhanced quinoidal resonance, increased spin density and strong intermolecular antiferromagnetic coupling, PBBT‐TT exhibits high intrinsic electrical conductivity and Seebeck coefficient, which showcases an outstanding power factor of 26.1 μW m−1 K−2 without doping. This achievement surpasses other neutral organic conjugated polymer and radical conductors, and is even comparable to some typical early‐stage doped polymers. Notably, PBBT‐TT exhibits remarkable ambient stability, retaining its initial thermoelectric performance over a 120‐day period. Our finding demonstrates that modulating the intermolecular spin interactions in open‐shell polymers through the introduction of strong proquinoidal units is an effective strategy for the development of doping‐free, intrinsically high‐performance polymer thermoelectric materials.

Precision multi-mode microwave spectroscopy of paramagnetic and rare-earth ion spin defects in single crystal calcium tungstate

We present experimental observations of dilute ion spin ensemble defects in a low-loss single crystal cylindrical sample of CaWO4 cooled to 30 mK in temperature. Crystal field perturbations were elucidated by constructing a dielectrically loaded microwave cavity resonator from the crystal. The resonator exhibited numerous whispering gallery modes with high Q-factors of up to 3×107, equivalent to a loss tangent of ∼3×10−8. The low loss allowed precision multi-mode spectroscopy of numerous high Q-factor photon–spin interactions. Measurements between 7 and 22 GHz revealed the presence of Gd3+, Fe3+, and another trace species, inferred to be rare-earth, at concentrations on the order of parts per billion. These findings motivate further exploration of prospective uses of this low-loss dielectric material for applications regarding precision and quantum metrology, as well as tests for beyond standard model physics.

Bi2O2.33/Bi4O5I2-heterojunction photocatalysts for adsorption and visible light-driven degradation of pharmaceutical pollutants

This study introduces the innovative Bi4O5I2/Bi2O2.33 heterojunction for diclofenac (DF) degradation. Pharmaceutical pollutants, especially DF, pose significant threats to water sources, necessitating efficient treatment methods. Bi2O2.33, renowned for its unique ferromagnetic properties, emerges as a promising photocatalyst for pollutant degradation. Bi4O5I2, known for strong visible light absorption and stability, holds potential for environmental applications. Interestingly, the inclusion of titanium dioxide (TiO2) in the composite catalysts significantly influences their observed ferromagnetic properties, as revealed by Electron Paramagnetic Resonance (EPR) spectroscopy, by influencing the interactions within the Bi4O5I2/Bi2O2.33 heterojunction and influencing its structure, morphology, and spin behavior. This interaction results in enhanced EPR and Ferromagnetic Resonance (FMR) signals, indicating intriguing spin interactions, polarization effects, charge transfers, surface dynamics, and stabilized magnetic domains. While the enhanced ferromagnetism holds promise for efficient charge separation and potential applications in environmental remediation, the expected boost in visible light-driven activity was not fully realized. This limitation is attributed to TiO2 inherent inability to directly absorb visible light, hindering its utilization for enhanced photocatalysis within the heterojunction. Nevertheless, these findings elucidate the multifaceted role of TiO2 in modulating the magnetic properties of these catalysts, offering valuable insights for future advancements in the design of advanced photocatalysts for effective environmental remediation.

Exchange coupling states of cobalt complexes to control proton-coupled electron transfer

The electrochemical proton reactivity of transition metal complexes receives significant attentions. A thorough understanding of proton-coupled electron transfer (PCET) pathways is essential for elucidating the mechanism behind a proton reduction reaction, and controlling the pathway is a key focus in the field of the catalyst development. Spin interactions within complexes, which arise during electron transfer, can affect significantly the PCET pathway. Herein, we explore the phenomenon of spin rearrangement during the electrochemical reorganization of high-spin cobalt complexes. Our findings reveal that opposing spin interactions, induced by different coordination environments, can alter the PCET pathway. Finally, detailed analysis of the PCET pathway allows us to propose mechanisms for proton reduction in high-spin cobalt complexes.

Gibbs state sampling via cluster expansions

Gibbs states (i.e., thermal states) can be used for several applications such as quantum simulation, quantum machine learning, quantum optimization, and the study of open quantum systems. Moreover, semi-definite programming, combinatorial optimization problems, and training quantum Boltzmann machines can all be addressed by sampling from well-prepared Gibbs states. With that, however, comes the fact that preparing and sampling from Gibbs states on a quantum computer are notoriously difficult tasks. Such tasks can require large overhead in resources and/or calibration even in the simplest of cases, as well as the fact that the implementation might be limited to only a specific set of systems. We propose a method based on sampling from a quasi-distribution consisting of tensor products of mixed states on local clusters, i.e., expanding the full Gibbs state into a sum of products of local “Gibbs-cumulant” type states easier to implement and sample from on quantum hardware. We begin with presenting results for 4-spin linear chains with XY spin interactions, for which we obtain the ZZ dynamical spin-spin correlation functions and dynamical structure factor. We also present the results of measuring the specific heat of the 8-spin chain Gibbs state ρ8.

Molecular influence on nuclear-quadrupole-coupling effects in laser induced alignment.

We computationally studied the effect of nuclear-quadrupole interactions on the field-free impulsive alignment of different asymmetric-top molecules. Our analysis is focused on the influence of the hyperfine- and rotational-energy-level structures. These depend on the number of nuclear spins, the rotational constants, and the symmetry of the tensors involved in the nuclear spin and external field interactions. Comparing the prototypical large-nuclear-spin molecules iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, and 2,5-diiodobenzonitrile, we demonstrate that the magnitude of the hyperfine splittings compared to the rotational-energy splittings plays a crucial role in the spin-rotational dynamics after the laser pulse. Moreover, we point out that the impact of the quadrupole coupling on the rotational dynamics decreases when highly excited rotational states dominate the dynamics.

Lieb-Schultz-Mattis Theorem for 1D Quantum Magnets with Antiunitary Translation and Inversion Symmetries.

We study quantum many-body systems in the presence of an exotic antiunitary translation or inversion symmetry involving time reversal. Based on a symmetry-twisting method and spectrum robustness, we propose that a half-integer spin chain that respects any of these two antiunitary crystalline symmetries in addition to the discrete Z_{2}×Z_{2} global spin-rotation symmetry must either be gapless or possess degenerate ground states. This explains the gaplessness of a class of chiral spin models not indicated by the Lieb-Schultz-Mattis theorem and its known extensions. Moreover, we present symmetry classes with minimal sets of generators that give nontrivial Lieb-Schultz-Mattis-type constraints, argued by the bulk-boundary correspondence in 2D symmetry-protected topological phases as well as lattice homotopy. Our results for detecting the ingappability of 1D quantum magnets from the interplay between spin-rotation symmetries and magnetic space groups are applicable to systems with a broader class of spin interactions, including Dzyaloshinskii-Moriya and triple-product interactions.

Tuning the Spin Interaction in Nonplanar Organic Diradicals through Mechanical Manipulation.

Open-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhibit spin delocalization, form extended collective states, and respond to the flexibility of the molecular backbones. However, they are also highly reactive, requiring structural strategies to protect the radical states from reacting with the environment. Here, we demonstrate that the open-shell ground state of the diradical 2-OS survives on a Au(111) substrate as a global singlet formed by two unpaired electrons with antiparallel spins coupled through a conformational-dependent interaction. The 2-OS molecule is a "protected" derivative of the Chichibabin's diradical, featuring a nonplanar geometry that destabilizes the closed-shell quinoidal structure. Using scanning tunneling microscopy (STM), we localized the two interacting spins at the molecular edges, and detected an excited triplet state a few millielectronvolts above the singlet ground state. Mean-field Hubbard simulations reveal that the exchange coupling between the two spins strongly depends on the torsional angles between the different molecular moieties, suggesting the possibility of influencing the molecule's magnetic state through structural changes. This was demonstrated here using the STM tip to manipulate the molecular conformation, while simultaneously detecting changes in the spin excitation spectrum. Our work suggests the potential of these PAHs as all-carbon spin-crossover materials.

Spin Dynamics of Radical Pairs Using the Stochastic Schrödinger Equation in MolSpin.

The chemical reactivity of radical pairs is strongly influenced by the interactions of electronic and nuclear spins. A detailed understanding of these effects requires a quantum description of the spin dynamics that considers spin-dependent reaction rates, interactions with external magnetic fields, spin-spin interactions, and the loss of spin coherence caused by coupling to a fluctuating environment. Modeling real chemical and biochemical systems, which frequently involve radicals with multinuclear spin systems, poses a severe computational challenge. Here, we implement a method based on the stochastic Schrödinger equation in the software package MolSpin. Large electron-nuclear spin systems can be simulated efficiently, with asymmetric spin-selective recombination reactions, anisotropic hyperfine interactions, and nonzero exchange and dipolar couplings. Spin-relaxation can be modeled using the stochastic time-dependence of spin interactions determined by molecular dynamics and quantum chemical calculations or by allowing rate coefficients to be explicitly time-dependent. The flexibility afforded by this approach opens new avenues for exploring the effects of complex molecular motions on the spin dynamics of chemical transformations.

Nitroxide Spin Labels for Exploring Relationships Between Molecular Structure, Microenvironment and EPR Parameters: A Mini-review Dedicated to Carlo Corvaja

AbstractThis mini-review is dedicated to Carlo Corvaja (University of Padova) in recognition of his important contributions to the study of biomimetic donor–acceptor model dyads and triads and to the understanding of spin exchange in excited fullerene–nitroxide derivatives. We report on attractive examples of multi-frequency and multi-resonance EPR spectroscopy, highlighting recent work in Padova and Berlin/Mülheim. The examples selected include TR-EPR, ENDOR, and EDNMR experiments on photoexcited spin-labeled macromolecules, such as fullerene–nitroxide complexes or photosynthetic bacterial reaction centers, which were optionally NO spin-labeled. From the spin interaction parameters measured, detailed information about structure and dynamics of macromolecules embedded in liquid-solution or solid-state microenvironments could be extracted.

Low Temperature Plasma-Assisted Double Anodic Dissolution: A New Approach for the Synthesis of GdFeO3 Perovskite Nanoparticles.

Orthorhombic perovskite GdFeO3 nanostructures are promising materials with multiferroic properties. In this study, a new low-temperature plasma-assisted approach is developed via dual anodic dissolution of solid metallic precursors for the preparation of perovskite GdFeO3 nanoparticles (NPs) that can be collected both as colloids as well as deposited as a thin film on a substrate. Two solid metallic foils of Gd and Fe are used as precursors, adding to the simplicity and sustainability of the method. The formation of the orthorhombic perovskite GdFeO3 phase is supported by high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman measurements, while a uniform elemental distribution of Gd, Fe, and O is confirmed by energy dispersive X-ray spectroscopy, proving the successful preparation of ternary compound NPs. The magnetic properties of the NPs show zero remnant magnetization typical of antiferromagnetic materials, and saturation at high fields that can be caused by spin interaction between Gd and Fe magnetic sublattices. The formation mechanism of ternary compound NPs in this novel plasma-assisted method is also discussed. This method is also modified to demonstrate the direct one-step deposition of thin films, opening up opportunities for their future applications in the fabrication of magnetic memory devices and gas sensors.

Molecule-Supported Magnetic-Atom Dimers on Au(111): Multiple Structures and Kondo Resonances

Magnetic-atom dimers on surface provide a powerful platform to study single spin interactions and qubit controls. They have been experimented on bare and thin-insulator-covered metallic surfaces, with strong and weak couplings between atoms and surfaces, respectively. If they are embedded in single molecules on surfaces, they may allow new geometric and electronic configurations as well as different coupling levels. But such system has rarely been studied. Here we report our scanning tunneling microscopy studies for molecule-supported magnetic-atom dimers on Au(111). Through on-surface reactions, Fe-Co dimers were embedded to porphyrin molecules in three different types. We observed zero-bias resonance in our scanning tunneling spectroscopy from one type with the Kondo temperature lower than Co-porphyrin molecules. Based on our density functional theory calculation results, atomic structures of three dimer structures were reproduced, and the observed Kondo behaviors were explained. Our study shows that the molecule supported magnetic-atom dimers can be a useful platform for studying spin physics and quantum information science.

Competing gauge fields and entropically driven spin liquid to spin liquid transition in non-Kramers pyrochlores.

Gauge theories are powerful theoretical physics tools that allow complex phenomena to be reduced to simple principles and are used in both high-energy and condensed matter physics. In the latter context, gauge theories are becoming increasingly popular for capturing the intricate spin correlations in spin liquids, exotic states of matter in which the dynamics of quantum spins never ceases, even at absolute zero temperature. We consider a spin system on a three-dimensional pyrochlore lattice where emergent gauge fields not only describe the spin liquid behavior at zero temperature but crucially determine the system's temperature evolution, with distinct gauge fields giving rise to different spin liquid phases in separate temperature regimes. Focusing first on classical spins, in an intermediate temperature regime, the system shows an unusual coexistence of emergent vector and tensor gauge fields where the former is known from classical spin ice systems while the latter has been associated with fractonic quasiparticles, a peculiar type of excitation with restricted mobility. Upon cooling, the system transitions into a low-temperature phase where an entropic selection mechanism depopulates the degrees of freedom associated with the tensor gauge field, rendering the system spin-ice-like. We further provide numerical evidence that in the corresponding quantum model, a spin liquid with coexisting vector and tensor gauge fields has a finite window of stability in the parameter space of spin interactions down to zero temperature. Finally, we discuss the relevance of our findings for non-Kramers magnetic pyrochlore materials.

Electronic excitations and spin interactions in chromium trihalides from embedded many-body wavefunctions

Although chromium trihalides are widely regarded as a promising class of two-dimensional magnets for next-generation devices, an accurate description of their electronic structure and magnetic interactions has proven challenging to achieve. Here, we quantify electronic excitations and spin interactions in CrX3 (X = Cl, Br, I) using embedded many-body wavefunction calculations and fully generalized spin Hamiltonians. We find that the three trihalides feature comparable d-shell excitations, consisting of a high-spin 4A2(t2g3eg0)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$({t}_{2g}^{3}{e}_{g}^{0})$$\\end{document} ground state lying 1.5–1.7 eV below the first excited state 4T2 (t2g2eg1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${t}_{2g}^{2}{e}_{g}^{1}$$\\end{document}). CrCl3 exhibits a single-ion anisotropy Asia = − 0.02 meV, while the Cr spin-3/2 moments are ferromagnetically coupled through bilinear and biquadratic exchange interactions of J1 = − 0.97 meV and J2 = − 0.05 meV, respectively. The corresponding values for CrBr3 and CrI3 increase to Asia = −0.08 meV and Asia= − 0.12 meV for the single-ion anisotropy, J1 = −1.21 meV, J2 = −0.05 meV and J1 = −1.38 meV, J2 = −0.06 meV for the exchange couplings, respectively. We find that the overall magnetic anisotropy is defined by the interplay between Asia and Adip due to magnetic dipole–dipole interaction that favors in-plane orientation of magnetic moments in ferromagnetic monolayers and bulk layered magnets. The competition between the two contributions sets CrCl3 and CrI3 as the easy-plane (Asia + Adip >0) and easy-axis (Asia + Adip <0) ferromagnets, respectively. The differences between the magnets trace back to the atomic radii of the halogen ligands and the magnitude of spin–orbit coupling. Our findings are in excellent agreement with recent experiments, thus providing reference values for the fundamental interactions in chromium trihalides.