Electron Spin Research Articles

Magnetically separable Z-scheme ZnFe2O4/MoS2 photocatalyst for boosting photo-Fenton degradation activity by a hole-mediated mechanism

The development of high-efficiency and robust photocatalysts is imperative and challenging in advanced oxidation processes (AOPs). Herein, magnetically separable ZnFe2O4/MoS2 photocatalyst was prepared by a simple hydrothermal method. The degradation characteristics of several organic pollutants (rhodamine B (RhB), methyl orange, methylene blue, and antibiotic tetracycline) were investigated with/without the addition of H2O2 under visible light irradiation. It is found that the synergistic effect of Z-scheme ZnFe2O4/MoS2 photocatalyst and photo-fenton-like reaction promotes the decomposition of H2O2, accelerates the separation efficiency of photogenerated electrons and holes, and thus improves the photocatalytic activity. The RhB photo-degradation of the constructed Z-scheme ZnFe2O4/MoS2 (96.3%) photocatalyst in the absence of H2O2 for 100min is better than that of MoS2 (74.8%) and ZnFe2O4 (6.2%), with a rate constant of 0.0332min-1. The slight amount of H2O2 boosts the photocatalytic performance significantly. Its degradation rate is 98.6% within 8min with the rate constant of 0.396min-1, 12 times higher than that of ZnFe2O4/MoS2 photocatalyst without H2O2. The magnetic separation, recycling stability and neutral solution process are also confirmed in ZnFe2O4/MoS2 system, indicating the enormous potential of this photocatalyst in environmental remediation and waste water treatment. The hole-mediated oxidation mechanism has been proposed instead of conventional active radicals of •OH based on the free radicals capture and electron spin resonance experiments. MoS2 plays a crucial role in facilitating the H2O2 decomposition and realizing the conversion circulation from Fe3+ to Fe2+ by the redox cycling as a co-catalyst. This study provides insights into the photocatalytic mechanism of Z-scheme photo-Fenton heterojunction photocatalysts, conducive to the development of high-efficient and stable photocatalysts in AOPs.

Regulating the Critical Intermediates of Dual-Atom Catalysts for CO2 Electroreduction.

Electrocatalysis is a very attractive way to achieve a sustainable carbon cycle by converting CO2 into organic fuels and feedstocks. Therefore, it is crucial to design advanced electrocatalysts by understanding the reaction mechanism of electrochemical CO2 reduction reaction (eCO2RR) with multiple electron transfers. Among electrocatalysts, dual-atom catalysts (DACs) are promising candidates due to their distinct electronic structures and extremely high atomic utilization efficiency. Herein, the eCO2RR mechanism and the identification of intermediates using advanced characterization techniques, with a particular focus on regulating the critical intermediates are systematically summarized. Further, the insightful understanding of the functionality of DACs originates from the variable metrics of electronic structures including orbital structure, charge distribution, and electron spin state, which influences the active sites and critical intermediates in eCO2RR processes. Based on the intrinsic relationship between variable metrics and critical intermediates, the optimized strategies of DACs are summarized containing the participation of synergistic atoms, engineering of the atomic coordination environment, regulation of the diversity of central metal atoms, and modulation of metal-support interaction. Finally, the challenges and future opportunities of atomically dispersed catalysts for eCO2RR processes are discussed.

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits.

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition-metal complexes via optically detected magnetic resonance (ODMR) mechanisms analogous to the diamond-nitrogen-vacancy color center. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are π-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realize a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimize radical-radical interactions in the ground state, generating π-systems with high diradical characters. We call them m-dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m-diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarization. The molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m-diradicals as molecular color centers.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA/cm2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance. This article is protected by copyright. All rights reserved.

Ligand Effects on the Spin Relaxation Dynamics and Coherent Manipulation of Organometallic La(II) Potential Qudits.

We present pulsed electron paramagnetic resonance (EPR) studies on three La(II) complexes, [K(2.2.2-cryptand)][La(Cp')3] (1), [K(2.2.2-cryptand)][La(Cp″)3] (2), and [K(2.2.2-cryptand)][La(Cptt)3] (3), which feature cyclopentadienyl derivatives as ligands [Cp' = C5H4SiMe3; Cp″ = C5H3(SiMe3)2; Cptt = C5H3(CMe3)2] and display a C3 symmetry. Long spin-lattice relaxation (T1) and phase memory (Tm) times are observed for all three compounds, but with significant variation in T1 among 1-3, with 3 being the slowest relaxing due to higher s-character of the SOMO. The dephasing times can be extended by more than an order of magnitude via dynamical decoupling experiments using a Carr-Purcell-Meiboom-Gill (CPMG) sequence, reaching 161 μs (5 K) for 3. Coherent spin manipulation is performed by the observation of Rabi quantum oscillations up to 80 K in this nuclear spin-rich environment (1H, 13C, and 29Si). The high nuclear spin of 139La (I = 7/2), and the ability to coherently manipulate all eight hyperfine transitions, makes these molecules promising candidates for application as qudits (multilevel quantum systems featuring d quantum states; d >2) for performing quantum operations within a single molecule. Application of HYSCORE techniques allows us to quantify the electron spin density at ligand nuclei and interrogate the role of functional groups to the electron spin relaxation properties.

Highly tunable ground and excited state excitonic dipoles in multilayer 2H-MoSe2

The fundamental properties of an exciton are determined by the spin, valley, energy, and spatial wavefunctions of the Coulomb-bound electron and hole. In van der Waals materials, these attributes can be widely engineered through layer stacking configuration to create highly tunable interlayer excitons with static out-of-plane electric dipoles, at the expense of the strength of the oscillating in-plane dipole responsible for light-matter coupling. Here we show that interlayer excitons in bi- and tri-layer 2H-MoSe2 crystals exhibit electric-field-driven coupling with the ground (1s) and excited states (2s) of the intralayer A excitons. We demonstrate that the hybrid states of these distinct exciton species provide strong oscillator strength, large permanent dipoles (up to 0.73 ± 0.01 enm), high energy tunability (up to ~200 meV), and full control of the spin and valley characteristics such that the exciton g-factor can be manipulated over a large range (from −4 to +14). Further, we observe the bi- and tri-layer excited state (2s) interlayer excitons and their coupling with the intralayer excitons states (1s and 2s). Our results, in good agreement with a coupled oscillator model with spin (layer)-selectivity and beyond standard density functional theory calculations, promote multilayer 2H-MoSe2 as a highly tunable platform to explore exciton-exciton interactions with strong light-matter interactions.

Demonstration of an energy-efficient Ising solver composed of Ovonic threshold switch (OTS)-based nano-oscillators (OTSNOs)

As there is an increasing need for an efficient solver of combinatorial optimization problems, much interest is paid to the Ising machine, which is a novel physics-driven computing system composed of coupled oscillators mimicking the dynamics of the system of coupled electronic spins. In this work, we propose an energy-efficient nano-oscillator, called OTSNO, which is composed of an Ovonic Threshold Switch (OTS) and an electrical resistor. We demonstrate that the OTSNO shows the synchronization behavior, an essential property for the realization of an Ising machine. Furthermore, we have discovered that the capacitive coupling is advantageous over the resistive coupling for the hardware implementation of an Ising solver by providing a larger margin of the variations of components. Finally, we implement an Ising machine composed of capacitively-coupled OTSNOs to demonstrate that the solution to a 14-node MaxCut problem can be obtained in 40 µs while consuming no more than 2.3 µJ of energy. Compared to a previous hardware implementation of the phase-transition nano-oscillator (PTNO)-based Ising machine, the OTSNO-based Ising machine in this work shows the performance of the increased speed by more than one order while consuming less energy by about an order.

Vanadium in silicon carbide: telecom-ready spin centres with long relaxation lifetimes and hyperfine-resolved optical transitions

Vanadium in silicon carbide (SiC) is emerging as an important candidate system for quantum technology due to its optical transitions in the telecom wavelength range. However, several key characteristics of this defect family including their spin relaxation lifetime (T1), charge state dynamics, and level structure are not fully understood. In this work, we determine the T1 of an ensemble of vanadium defects, demonstrating that it can be greatly enhanced at low temperature. We observe a large spin contrast exceeding 90% and long spin-relaxation times of up to 25 s at 100 mK, and of order 1 s at 1.3 K. These measurements are complemented by a characterization of the ensemble charge state dynamics. The stable electron spin furthermore enables high-resolution characterization of the systems’ hyperfine level structure via two-photon magneto-spectroscopy. The acquired insights point towards high-performance spin-photon interfaces based on vanadium in SiC.

Single-step parity check gate set for quantum error correction

A key requirement for an effective quantum error correction (QEC) scheme is that the physical qubits have error rates below a certain threshold. The value of this threshold depends on the details of the specific QEC scheme, and its hardware-level implementation. This is especially important with parity-check circuits, which are the fundamental building blocks of QEC codes. The standard way of constructing the parity check circuit is using a universal set of gates, namely sequential CNOT gates, single-qubit rotations and measurements. We exploit the insight that a QEC code does not require universal logic gates, but can be simplified to perform the sole task of error detection and correction. By building gates that are fundamental to QEC, we can boost the threshold and ease the experimental demands on the physical hardware. We present a rigorous formalism for constructing and verifying the error behavior of these gates, linking the physical measurement of a process matrix to the abstract error models commonly used in QEC analysis. This allows experimentalists to directly map the gates used in their systems to thresholds derived for a broad-class of QEC codes. We give an example of these new constructions using the model system of two nuclear spins, coupled to an electron spin, showing the potential benefits of redesigning fundamental gate sets using QEC primitives, rather than traditional gate sets reliant on simple single and two-qubit gates.

Bounds to electron spin qubit variability for scalable CMOS architectures

Spins of electrons in silicon MOS quantum dots combine exquisite quantum properties and scalable fabrication. In the age of quantum technology, however, the metrics that crowned Si/SiO2 as the microelectronics standard need to be reassessed with respect to their impact upon qubit performance. We chart spin qubit variability due to the unavoidable atomic-scale roughness of the Si/SiO2 interface, compiling experiments across 12 devices, and develop theoretical tools to analyse these results. Atomistic tight binding and path integral Monte Carlo methods are adapted to describe fluctuations in devices with millions of atoms by directly analysing their wavefunctions and electron paths instead of their energy spectra. We correlate the effect of roughness with the variability in qubit position, deformation, valley splitting, valley phase, spin-orbit coupling and exchange coupling. These variabilities are found to be bounded, and they lie within the tolerances for scalable architectures for quantum computing as long as robust control methods are incorporated.

The Adiabatic 1D Kinetic Equilibrium of the Electron Diffusion Region During Anti‐Parallel Magnetic Reconnection

AbstractAn earlier model of the electron distribution function accounts for the pressure anisotropy that develops in the inflow regions during anti‐parallel magnetic reconnection. However, the model is not applicable to the electron diffusion region (EDR), where the electron magnetic moments break as an adiabatic invariant. The earlier model is here generalized through the use of the current‐sheet adiabatic invariant of a 1D current layer, to become applicable also to the EDR. The new generalized model reproduces the main features of the EDR and its vicinity observed in a fully kinetic simulation, formally proving the 1D equilibrium relationship between the upstream electron pressure anisotropy and the EDR electron jets.

The Importance of Spin-Polarized Charge Reorganization in the Catalytic Activity of D-Glucose Oxidase.

The front cover artwork is provided by Prof. Ron Naaman's group at the Weizmann Institute of Science. The image shows that direct electron transfer through GOx is governed by electron spins, which result from the chiral-induced spin selectivity (CISS) effect. Read the full text of the Research Article at 10.1002/cphc.202400033.

All-optical spin access via a cavity-broadened optical transition in on-chip hybrid quantum photonics

Hybrid quantum photonic systems connect classical photonics to the quantum world and promise to deliver efficient light-matter quantum interfaces while leveraging the advantages of both, the classical and the quantum, subsystems. However, combining efficient, scalable photonics and solid-state quantum systems with desirable optical and spin properties remains a formidable challenge. In particular, the access to individual spin states and coherent mapping to photons remains unsolved for hybrid systems. In this paper, we demonstrate all-optical initialization and readout of the electron spin of a negatively charged silicon-vacancy center in a nanodiamond coupled to a silicon nitride photonic crystal cavity. We characterize relevant parameters of the coupled emitter-cavity system and determine the silicon-vacancy center’s spin-relaxation and spin-decoherence rate. Our results mark a key step towards the realization of a hybrid spin-photon interface based on silicon nitride photonics and the silicon-vacancy center’s electron spin in nanodiamonds with potential use for quantum networks, quantum communication, and distributed quantum computation. Published by the American Physical Society 2024

Coherent Microwave, Optical, and Mechanical Quantum Control of Spin Qubits in Diamond

AbstractDiamond has emerged as a highly promising platform for quantum network applications. Color centers in diamond fulfill the fundamental requirements for quantum nodes: they constitute optically accessible quantum systems with long‐lived spin qubits. Furthermore, they provide access to a quantum register of electronic and nuclear spin qubits and they mediate entanglement between spins and photons. All these operations require coherent control of the color center's spin state. This review provides a comprehensive overview of the state‐of‐the‐art, challenges, and prospects of such schemes, including high‐fidelity initialization, coherent manipulation, and readout of spin states. Established microwave and optical control techniques are reviewed, and moreover, emerging methods such as cavity‐mediated spin–photon interactions and mechanical control based on spin–phonon interactions are summarized. For different types of color centers, namely, nitrogen–vacancy and group‐IV color centers, distinct challenges persist that are subject of ongoing research. Beyond fundamental coherent spin qubit control techniques, advanced demonstrations in quantum network applications are outlined, for example, the integration of individual color centers for accessing (nuclear) multiqubit registers. Finally, the role of diamond spin qubits in the realization of future quantum information applications is described.

Natural Sunlight-Mediated Emodin Photoinactivation of Aeromonas hydrophila.

Aeromonas hydrophila can be a substantial concern, as it causes various diseases in aquaculture. An effective and green method for inhibiting A. hydrophila is urgently required. Emodin, a naturally occurring anthraquinone compound, was exploited as a photo-antimicrobial agent against A. hydrophila. At the minimum inhibitory concentration of emodin (256 mg/L) to inactivate A. hydrophilia in 30 min, an 11.32% survival rate was observed under 45 W white compact fluorescent light irradiation. In addition, the antibacterial activity under natural sunlight (0.78%) indicated its potential for practical application. Morphological observations demonstrated that the cell walls and membranes of A. hydrophila were susceptible to damage by emodin when exposed to light irradiation. More importantly, the photoinactivation of A. hydrophila was predominantly attributed to the hydroxyl radicals and superoxide radicals produced by emodin, according to the trapping experiment and electron spin resonance spectroscopy. Finally, a light-dependent reactive oxygen species punching mechanism of emodin to photoinactivate A. hydrophila was proposed. This study highlights the potential use of emodin in sunlight-mediated applications for bacterial control, thereby providing new possibilities for the use of Chinese herbal medicine in aquatic diseases prevention.

Rearranging Spin Electrons by Axial-Ligand-Induced Orbital Splitting to Regulate Enzymatic Activity of Single-Atom Nanozyme with Destructive d-π Conjugation.

Most of the nanozymes have been obtained based on trial and error, for which the application is usually compromised by enzymatic activity regulation due to a vague catalytic mechanism. Herein, a hollow axial Mo-Pt single-atom nanozyme (H-MoN5@PtN4/C) is constructed by a two-tier template capture strategy. The axial ligand can induce Mo 4d orbital splitting, leading to a rearrangement of spin electrons (↑ ↑ → ↑↓) to regulate enzymatic activity. This creates catalase-like activity and enhances oxidase-like activity to catalyze cascade enzymatic reactions (H2O2 → O2 → O2•-), which can overcome tumor hypoxia and accumulate cytotoxic superoxide radicals (O2•-). Significantly, H-MoN5@PtN4/C displays destructive d-π conjugation between the metal and substrate to attenuate the restriction of orbitals and electrons. This markedly improves enzymatic performance (catalase-like and oxidase-like activity) of a Mo single atom and peroxidase-like properties of a Pt single atom. Furthermore, the H-MoN5@PtN4/C can deplete overexpressed glutathione (GSH) through a redox reaction, which can avoid consumption of ROS (O2•- and •OH). As a result, H-MoN5@PtN4/C can overcome limitations of a complex tumor microenvironment (TME) for tumor-specific therapy based on TME-activated catalytic activity.

Entanglement of nanophotonic quantum memory nodes in a telecom network

A key challenge in realizing practical quantum networks for long-distance quantum communication involves robust entanglement between quantum memory nodes connected by fibre optical infrastructure1–3. Here we demonstrate a two-node quantum network composed of multi-qubit registers based on silicon-vacancy (SiV) centres in nanophotonic diamond cavities integrated with a telecommunication fibre network. Remote entanglement is generated by the cavity-enhanced interactions between the electron spin qubits of the SiVs and optical photons. Serial, heralded spin-photon entangling gate operations with time-bin qubits are used for robust entanglement of separated nodes. Long-lived nuclear spin qubits are used to provide second-long entanglement storage and integrated error detection. By integrating efficient bidirectional quantum frequency conversion of photonic communication qubits to telecommunication frequencies (1,350 nm), we demonstrate the entanglement of two nuclear spin memories through 40 km spools of low-loss fibre and a 35-km long fibre loop deployed in the Boston area urban environment, representing an enabling step towards practical quantum repeaters and large-scale quantum networks.

Protective effect of luteolin against oxidative stress‑mediated cell injury via enhancing antioxidant systems.

Physiological stress such as excessive reactive oxygen species (ROS) production may contribute normal fibroblasts activation into cancer‑associated fibroblasts, which serve a crucial role in certain types of cancer such as pancreatic, breast, liver and lung cancer. The present study aimed to examine the cytoprotective effects of luteolin (3',4',5,7‑tetrahydroxyflavone) against hydrogen peroxide (H2O2)‑generated oxidative stress in lung fibroblasts. To examine the effects of luteolin against H2O2‑induced damages, cell viability, sub‑G1 cell population, nuclear staining with Hoechst 33342, lipid peroxidation and comet assays were performed. To evaluate the effects of luteolin on the protein expression level of apoptosis, western blot assay was performed. To assess the antioxidant effects of luteolin, detection of ROS using H2DCFDA staining, O2‑ and ·OH using electron spin resonance spectrometer and antioxidant enzyme activity was performed. In a cell‑free chemical system, luteolin scavenges superoxide anion and hydroxyl radical generated by xanthine/xanthine oxidase and the Fenton reaction (FeSO4/H2O2). Furthermore, Chinese hamster lung fibroblasts (V79‑4) treated with H2O2 showed a significant increase in cellular ROS. Intracellular ROS levels and damage to cellular components such as lipids and DNA in H2O2‑treated cells were significantly decreased by luteolin pretreatment. Luteolin increased cell viability, which was impaired following H2O2 treatment and prevented H2O2‑mediated apoptosis. Luteolin suppressed active caspase‑9 and caspase‑3 levels while increasing Bcl‑2 expression and decreasing Bax protein levels. Additionally, luteolin restored levels of glutathione that was reduced in response to H2O2. Moreover, luteolin enhanced the activity and protein expressions of superoxide dismutase, catalase, glutathione peroxidase, and heme oxygenase‑1. Overall, these results indicated that luteolin inhibits H2O2‑mediated cellular damage by upregulating antioxidant enzymes.

Microcontroller-Optimized Measurement Electronics for Coherent Control Applications of NV Centers.

Long coherence times at room temperature make the NV center a promising candidate for quantum sensors and quantum computers. The necessary coherent control of the electron spin triplet in the ground state requires microwave π pulses in the nanosecond range, obtained from the Rabi oscillation of the mS spin states of the magnetic resonances of the NV centers. Laboratory equipment has a high temporal resolution for these measurements but is expensive and, therefore, uninteresting for fields such as education. In this work, we present measurement electronics for NV centers that are optimized for microcontrollers. It is shown that the Rabi frequency is linear to the output of the digital-to-analog converter (DAC) and is used to adapt the time length π of the electron spin flip, to the limited pulse width resolution of the microcontroller. This was achieved by breaking down the most relevant functions of conventional laboratory devices and replacing them with commercially available integrated components. The result is a cost-effective handheld setup for coherent control applications of NV centers.

Development of the Time-Independent Methods for the Cl + H2/F + HD Reaction Using Hyper-Spherical Coordinates Including (Full) Spin-Orbit Characteristics.

Recently, a combined study of high-resolution molecular crossed beam experiment and accurate full-dimensional time-dependent theory, including full spin-orbit characteristics on the effect of electronic spin and orbital angular momenta in the F + HD reaction, was reported by some of us, focusing on the partial wave resonance phenomenon (Science 2021, 371, 936-940). It revealed that the time-dependent theory could explain all of the details observed in the high-resolution experiment. Here, we develop two time-independent close-coupling methods using hyperspherical coordinates, including the two-state model, where only a part of the spin-orbit characteristics is considered, and the six-state model, where the full spin-orbit characteristics is considered. With these two newly developed theoretical models and the adiabatic theoretical model, the detailed reaction dynamics of the F + HD (v = 0, j = 0) reaction and the Cl + H2 (v = 0, j = 0) reaction are investigated and compared. Some of the results are compared with the time-dependent quantum wave packet theory and the experimental observations, and good agreements have been obtained, which suggests the validity of the pure-procession approximation in the six-state model using different theoretical methods. This work demonstrates the ability of the reactive scattering theory including full spin-orbit characteristics for describing the reactions of a halogen atom plus hydrogen molecule and its isotopologues.