High Electron Spin Research Articles

Effect of dilute nitride GaNAs quantum well thickness on spin amplification dynamics of tunnel-coupled InAs quantum dots

Electron spin dynamics of dilute nitride GaNAs quantum well (QW)-InAs quantum dots (QDs) tunnel-coupled structures having different QW thicknesses were studied via circularly polarized time-resolved photoluminescence. The rate equation fitting considering a capture of QD electron spins by the GaNAs localized states via tunnel transfer revealed that the spin amplification dynamics of the QDs depended on the QW thickness. For the QW thickness of 5 nm, although the temporal amplification of QD electron spin polarization was slow owing to the weak wavefunction coupling between the QW and QD, the long duration of high electron spin polarization was observed because of the suppressed capture of QD majority spins relative to the efficient removal of QD minority spins. When the QW thickness increased from 5 to 20 nm, the strong spin filtering in GaNAs and strong wavefunction coupling led to the fast amplification of QD electron spin polarization with high initial spin polarization. However, the spin polarization rapidly decays after the amplification owing to the removal of both QD majority and minority spins, originating from many effective localized states. These results indicate that the time-dependent QD electron spin polarization and the resultant spin amplification can be widely tuned by changing the thickness of the tunnel-coupled GaNAs QW.

Macroscopic sample shape effect on pulse electron double resonance (PELDOR) signal

Pulse electron double resonance (PELDOR), also called double electron–electron resonance (DEER), is a technique capable of measuring the strength of electron spin dipolar interactions, revealing spin–spin distance distributions in ordered and disordered solid materials. Previous work has shown that PELDOR signals acquire an out-of-phase component under conditions of high electron spin polarization, such as at low temperatures and high fields. In this paper, we show theoretically and experimentally that the size and sign of this effect depends on the macroscopic shape of the sample and its orientation in the external magnetic field. This effect is caused by dipolar interactions between distant spins and provides new insights into the fundamental physics of PELDOR.

Formation of Ohmic contacts between ferromagnetic Cr2Ge2Te6 and two-dimensional metals

As a ferromagnetic semiconductor, two-dimensional (2D) Cr2Ge2Te6 holds significant implications for electronic and spintronic devices. To achieve 2D electronics, it is essential to integrate Cr2Ge2Te6 with 2D electrodes to form Schottky-barrier-free Ohmic contacts with enhanced carrier injection efficiency. Herein, by using first-principles calculations based on density-functional theory, we systematically investigate the structural, energetic, electronic and magnetic properties of 2D heterojunctions by combining Cr2Ge2Te6 with a series of 2D metals, including graphene, ZrCl, NbS2, TaS2, TaSe2, Zn3C2, Hg3C2, and Zr2N. Results show that NbS2, TaS2, TaSe2, Zn3C2, Hg3C2, and Zr2N form Ohmic contacts with Cr2Ge2Te6, in contrast to graphene and ZrCl that exhibit a finite Schottky barrier. By examining the tunneling barriers and Fermi level shift, we reveal that the heterojunctions with Zn3C2 and Hg3C2 as electrodes exhibit advantages of both high electron injection efficiency and spin injection efficiency, for which an apparent decrease of the magnetic moment of Cr atoms in Cr2Ge2Te6 can be observed. These findings not only provide physical insights into the role of interfacial interaction in regulating the physical properties of 2D heterojunctions, but also pave way for the development of high-performance spintronic nanodevices for practical implementation.

EPR and Related Magnetic Resonance Imaging Techniques in Cancer Research.

Imaging tumor microenvironments such as hypoxia, oxygenation, redox status, and/or glycolytic metabolism in tissues/cells is useful for diagnostic and prognostic purposes. New imaging modalities are under development for imaging various aspects of tumor microenvironments. Electron Paramagnetic Resonance Imaging (EPRI) though similar to NMR/MRI is unique in its ability to provide quantitative images of pO2 in vivo. The short electron spin relaxation times have been posing formidable challenge to the technology development for clinical application. With the availability of the narrow line width trityl compounds, pulsed EPR imaging techniques were developed for pO2 imaging. EPRI visualizes the exogenously administered spin probes/contrast agents and hence lacks the complementary morphological information. Dynamic nuclear polarization (DNP), a phenomenon that transfers the high electron spin polarization to the surrounding nuclear spins (1H and 13C) opened new capabilities in molecular imaging. DNP of 13C nuclei is utilized in metabolic imaging of 13C-labeled compounds by imaging specific enzyme kinetics. In this article, imaging strategies mapping physiologic and metabolic aspects in vivo are reviewed within the framework of their application in cancer research, highlighting the potential and challenges of each of them.

Study of Tricalcium Phosphate Ceramics Doped with Gadolinium Ions with Various EPR Techniques

Tricalcium phosphate (TCP)-based materials, such as β-Ca3(PO4)2 doped with rare earth ions (RE), have shown applications as biomaterials, lighting emitting materials, scintillating materials, in vivo imaging probes, and thermoluminescent dosimeters. Their properties are found to be dependent on the distribution of RE3+ on Ca2+ sites that can be controlled by pulsed electron paramagnetic resonance (EPR) and electron spin echo envelop modulation (ESEEM) experiments. The main spectroscopic parameters (spin Hamiltonian values) of Gd3+ and nitrogen impurity centers are quantitatively determined (g-factor, the fine structure parameters D and E, the hyperfine constants A) as well as dynamic characteristics: spin–lattice T1 and spin–spin T2 relaxation times. Based on the analysis of the EPR datasets, the interatomic distance between Gd3+ and 31P was estimated in the dipole–dipole approximation. Two structurally nonequivalent Gd3+ positions in the β-TCP structure have been identified. The obtained valuable results demonstrate applicability of modern EPR techniques to characterize Gd-TCP systems despite the powder structure of the material and high electron spin S = 7/2 of Gd3+ ions.

Edge magnetism of triangular graphene nanoflakes embedded in hexagonal boron nitride

Graphene nanoflakes (GNFs), with intriguing zigzag edge magnetism, have great potential for the application in high-speed and low-power nanoelectronics and spintronics. However, scattering from edge defects can substantially degrade this novel edge magnetism. Precisely controlled growth of GNFs with zigzag edges on dielectric substrates to suppress edge defect scattering is still challenging. Herein, we report the successful synthesis of triangular zigzag-edged GNFs via epitaxy on hexagonal boron nitride (h-BN) templates. Further magnetic measurement results indicate the triangular zigzag-edged GNFs embedded in h-BN can induce the magnetization with a magnitude of 1e-4 emu/g at room temperature. Additionally, density functional theory calculations address such magnetic orderings originating from the superexchange interactions among local “unpaired” electrons located in the zigzag C−BN interface. Our in-plane hetero-integration approach to the template-epitaxial growth of GNFs on the pre-etched h-BN provides a promising platform for experimentally achieving GNFs with high electron spin states, which are highly desired for next-generation spintronics and nanoelectronics.

Insights into the underlying effect of Fe vacancy defects on the adsorption affinity of goethite for arsenic immobilization

Goethite is a commonly found iron (hydr)oxide in soils and sediments that has been proven to possess abundant defects in structures. However, the underlying impact of these defects in goethite on arsenic immobilization remains unclear. In this study, goethite samples with abundant, moderate, and sparse defects were synthesized to evaluate their arsenic adsorption capacities. The characteristics of the defects in goethite were investigated by extended X-ray absorption fine structure (EXAFS), high angle annular dark field-scanning transmission electron microscopy-energy dispersion spectrum (HAADF-STEM-EDS) mapping, vibrating-sample magnetometry (VSM), and electron spin resonance (ESR). The characterization analysis revealed that the defects in as-synthesized goethite primarily existed in the form of Fe vacancies. Batch experiments demonstrated that the adsorption capacities of defect-rich goethite for As(V) and As(III) removal were 10.2 and 22.1 times larger than those of defect-poor goethite, respectively. The origin of the impact of Fe defects on arsenic immobilization was theoretically elucidated using density functional theory (DFT) calculations. The enhanced adsorption of goethite was attributed to the improvement of the arsenic affinity due to the Fe vacancy defect, thus considerably promoting arsenic immobilization. The findings of this study provide important insight into the migration and fate of arsenic in naturally occurring iron (hydr)oxides.

3d Metal Complexes in T-shaped Geometry as a Gateway to Metalloradical Reactivity.

ConspectusLow-valent, low-coordinate 3d metal complexes represent a class of extraordinarily reactive compounds that can act as reagents and catalysts for challenging bond-activation reactions. The pursuit of these electron-deficient metal complexes in low oxidation states demands ancillary ligands capable of providing not only energetic stabilization but also sufficiently high steric bulk at the metal center. From this perspective, pincer ligands are particularly advantageous, as their prearranged, meridional coordination mode scaffolds the active center while the substituents of the peripheral donor atoms provide effective steric shielding for the coordination sphere. In a T-shaped geometry, the transition metal complexes possess a precisely defined vacant coordination site, which, combined with the often observed high-spin electron configuration, exhibits unusually high selectivity of these compounds with respect to one-electron redox chemistry. In light of the intractable reaction pathways typically observed with related electronically unsaturated 3d transition metal complexes, the pincer coordination mode enables the isolation of low-valent compounds with more controlled and unique reactivity. We have thus investigated a series of T-shaped metal(I) complexes using three different types of pincer ligands, which may be regarded as "metalloradicals" due to their selectively exposed unpaired electrons.These compounds display remarkably high thermal stability and represent rarely observed "naked" monovalent metal species featuring both monomeric and dimeric structures. Extensive reactivity studies using various organic substrates highlight a strong tendency of these paramagnetic compounds to undergo one-electron oxidation, leading to the isolation of a plethora of metal(II) species with reduced organic ligands as unusual structural elements. The exploration of C2 symmetric T-shaped Ni(I) complexes as asymmetric catalysts also shows success in enantioselective hydrodehalogenation of geminal dihalogenides. In addition, this specific class of low-valent, low-coordinate complexes can be further diversified by introducing redox-active pincer ligands or building homobimetallic systems with two T-shaped units.This Account focuses on the discussion of selected examples of iron, cobalt, and nickel pincer complexes bearing a [P,N,P] or [N,N,N] donor set; however, their electronic structure and radical-type reactivity can be broadly extended to other pincer systems. The availability of various types of pincer ligands should allow fine-tuning of the reactivity of the T-shaped complexes. Given the unprecedented reactivity observed with these compounds, we expect the studies of T-shaped 3d metal complexes to be a fertile field for advancing base metal catalysis.

Photocatalytic Oxidation of Acid Orange 10 dye Molecules using Cerium Oxide Nanosphere Particles under Ultraviolet and Visible Light Irradiations

Exploration of semiconductors in the field of photocatalysis plays a crucial role in energy and environmental remediation in particular oxidation/reduction of toxic organic contaminants from water and wastewater. The present research work aims on synthesis of pristine CeO2nanoparticles by precipitation method and was thoroughly characterized by Fourier Transform Infrared spectroscopy, X-ray Diffraction, UV-vis-Diffuse Reflectance Spectroscopy, High Resolution Scanning Electron Microscopy, EDAX and Electron Spin Resonance techniques. The band gap energy (Ebg) was found to be 3.19 eV. The synthesized nanomaterials showed spherical morphology and the particles size ranged from 50-93 nm. The insitu generation of ·OH radicals was confirmed from ESR studies. The synthesized CeO2nanospheres was evaluatedin photocatalytic oxidation of an azo dye Acid orange 10 under Ultraviolet and visible light irradiations. Experimental studies such as pH, catalyst amount and effect of initial dye concentration were also studied. Kinetic studies indicate the photo reaction follows pseudo-first order rate equation. The photocatalytic oxidation of dye molecules were monitored by UV-visible spectroscopy and COD analyses. The level of chemical oxygen demand (COD) of the photodegraded samples decreases in both the photocatalytic systems indicating that dye molecules readily degraded under present experimental conditions.Effect of electrolytes like MgSO4,KCl, Na2CO3 and NaHCO3 were also investigated to check interference of inorganic anions on photocatalytic oxidation of dye molecules using CeO2 nanospheres. Finally, the prepared catalyst was checked for its reusability and the photocatalyst exhibited better photocatalytic activity evenafter three cycles of regeneration.Copyright © VBRI Press.

Laser cooling of transition-metal atoms

We propose the application of laser cooling to a number of transition-metal atoms, allowing numerous bosonic and fermionic atomic gases to be cooled to ultra-low temperatures. The non-zero electron orbital angular momentum of these atoms implies that strongly atom-state-dependent light-atom interactions occur even for light that is far-detuned from atomic transitions. At the same time, many transition-metal atoms have small magnetic dipole moments in their low-energy states, reducing the rate of dipolar-relaxation collisions. Altogether, these features provide compelling opportunities for future ultracold-atom research. Focusing on the case of atomic titanium, we identify the metastable $a ^5F_5$ state as supporting a $J \rightarrow J+1$ optical transition with properties similar to the D2 transition of alkali atoms, and suited for laser cooling. The high total angular momentum and electron spin of this state suppresses leakage out of the the nearly closed optical transition to a branching ratio estimated below $\sim 10^{-5}$. Following the pattern exemplified by titanium, we identify optical transitions that are suited for laser cooling of elements in the scandium group (Sc, Y, La), the titanium group (Ti, Zr), the vanadium group (V, Nb), the manganese group (Mn, Tc), and the iron group (Fe, Ru).

Formation of the High-Spin S2 State Related to the Extrinsic Proteins in the Oxygen Evolving Complex of Photosystem II.

The high-spin S2 state was investigated with photosystem II (PSII) from spinach, Thermosynechococcus vulcanus, and Cyanidioschyzon merolae. In extrinsic protein-depleted PSII, high-spin electron paramagnetic resonance (EPR) signals were not detected in either species, whereas all species showed g ∼ 5 signals in the presence of a high concentration of Ca2+ instead of the multiline signal. In the intact and PsbP/Q-depleted PSII from spinach, the g = 4.1 EPR signal was detected. These results show that formation of the high-spin S2 state of the manganese cluster is regulated by the extrinsic proteins through a charge located near the Mn4 atom in the Mn4CaO5 cluster but is independent of the intrinsic proteins. The shift to the g ∼ 5 state is caused by tilting of the z-axis in the Mn4 coordinates through hydrogen bonds or external divalent cations. The structural modification may allow insertion of an oxygen atom during the S2-to-S3 transition.

Singlet oxygen mediated the selective removal of oxytetracycline in C/Fe3C/Fe0 system as compared to chloramphenicol

Reactive oxygen species (ROS) production for Fe0 is limited because of the formed iron corrosion products. In this study, C/Fe3C/Fe0 composite which produces enhanced ROS has been specifically designed and fabricated to remove typical antibiotics (i.e., oxytetracycline (OTC) and chloramphenicol (CAP)) as a heterogeneous Fenton-like catalyst. The C/Fe3C/Fe0 composite demonstrated excellent performance for both OTC and CAP removal as compared with Fe0 and biochar. Furthermore, X-ray photoelectron spectrometry, Fourier transform infrared spectrometry, high performance liquid chromatography-mass spectra and electron spin resonance analyses were conducted to elucidate the adsorption and degradation mechanisms. The adsorption of OTC and CAP was mainly dominated by H bonds and the electron-acceptor-acceptor on the surface of the C/Fe3C/Fe0 composite, respectively. In particular, OH simultaneously induced the degradation of OTC and CAP, while 1O2 presented the selective oxidation to OTC. More specifically, the degradation of OTC over C/Fe3C/Fe0 was stronger and faster than that of CAP, leading to 65.84% and 16.84% of removal efficiency for OTC and CAP, respectively. Furthermore, C/Fe3C/Fe0 exhibited superior reusability and stability after regeneration, but regenerated Fe0 almost lost its reactivity. Therefore, the efficiency in situ generation of 1O2 using C/Fe3C/Fe0 would shed new light on the selective oxidation of aqueous organic compounds.

Materials design of Kitaev spin liquids beyond the Jackeli–Khaliullin mechanism

The Kitaev spin liquid provides a rare example of well-established quantum spin liquids in more than one dimension. It is obtained as the exact ground state of the Kitaev spin model with bond-dependent anisotropic interactions. The peculiar interactions can be yielded by the synergy of spin-orbit coupling and electron correlations for specific electron configuration and lattice geometry, which is known as the Jackeli–Khaliullin mechanism. Based on this mechanism, there has been a fierce race for the materialization of the Kitaev spin liquid over the last decade, but the candidates have been still limited mostly to 4d- and 5d-electron compounds including cations with the low-spin d5 electron configuration, such as Ir4+ and Ru3+. Here we discuss recent efforts to extend the material perspective beyond the Jackeli–Khaliullin mechanism, by carefully reexamining the two requisites, formation of the jeff = 1/2 doublet and quantum interference between the exchange processes, for not only d- but also f-electron systems. We present three examples: the systems including Co2+ and Ni3+ with the high-spin d7 electron configuration, Pr4+ with the f1-electron configuration, and polar asymmetry in the lattice structure. In particular, the latter two are intriguing since they may realize the antiferromagnetic Kitaev interactions, in contrast to the ferromagnetic ones in the existing candidates. This partial overview would stimulate further material exploration of the Kitaev spin liquids and its topological properties due to fractional excitations.

Photonic-Crystal Josephson Traveling-Wave Parametric Amplifier

An amplifier combining noise performances as close as possible to the quantum limit with large bandwidth and high saturation power is highly desirable for many solid state quantum technologies such as high fidelity qubit readout or high sensitivity electron spin resonance for example. Here we introduce a new Traveling Wave Parametric Amplifier based on Superconducting QUantum Interference Devices. It displays a 3 GHz bandwidth, a -102 dBm 1-dB compression point and added noise near the quantum limit. Compared to previous state-of-the-art, it is an order of magnitude more compact, its characteristic impedance is in-situ tunable and its fabrication process requires only two lithography steps. The key is the engineering of a gap in the dispersion relation of the transmission line. This is obtained using a periodic modulation of the SQUID size, similarly to what is done with photonic crystals. Moreover, we provide a new theoretical treatment to describe the non-trivial interplay between non-linearity and such periodicity. Our approach provides a path to co-integration with other quantum devices such as qubits given the low footprint and easy fabrication of our amplifier.

Demonstration of NV-detected ESR spectroscopy at 115 GHz and 4.2 T

High frequency electron spin resonance (ESR) spectroscopy is an invaluable tool for identification and characterization of spin systems. Nanoscale ESR using the nitrogen-vacancy (NV) center has been demonstrated down to the level of a single spin. However, NV-detected ESR has exclusively been studied at low magnetic fields, where the spectral overlap prevents clear identification of spectral features. In this work, we demonstrate NV-detected ESR measurements of single-substitutional nitrogen impurities in diamond at a NV Larmor frequency of 115 GHz and the corresponding magnetic field of 4.2 T. The NV-ESR measurements utilize a double electron-electron resonance sequence and are performed using both ensemble and single NV spin systems. In the single NV experiment, chirp pulses are used to improve the population transfer and for NV-ESR measurements. This work provides the basis for NV-based ESR measurements of external spins at high magnetic fields.

Effect of N-Amide Substitution on Antioxidative Activities of Melatonin Derivatives

Five N-amide substituted melatonin (MLT) derivatives were synthesized and evaluated for antioxidative activities, and compounds 9–12 showed higher electron spin resonance (ESR) response than MLT. 4-Bromobenzoyl and naphthoyl derivatives (10 and 11) presented stronger hydroxyl radical inhibitory effect than MLT in Fenton reaction. The substitution at the N1-position on the MLT core structure with acetyl (8), benzoyl (9), 4-bromobenzoyl (10), and naphthoyl (11) and N2-substitution with 4-bromobenzoyl (12) decreased the reducing power of the derivatives in ferric reducing antioxidant power (FRAP) assay. Compounds 8–11 also presented lower antioxidant capacity than their parent compound in 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) disodium salt (ABTS) assay; whereas, compound 12 presented radical scavenging activity similarly to MLT. All aryl derivatives (9–12) showed higher ability to quench peroxyl radicals than MLT about three times, especially the benzoylated derivatives (9 and 10) that presented the highest ability in oxygen radical absorbance capacity (ORAC) assay.

Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex

The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.

Reproducing benchmark potential energy curves of molecular bond dissociation with small complete active space aided with density and density-matrix functional corrections.

Various effects of electron correlation accompany molecular bond dissociation, which makes the efficient calculation of potential energy curves a notoriously difficult problem. In an attempt to reliably reproduce both absolute energies and shapes of the benchmark dissociation curves, calculations with the combined CASΠDFT method are carried out for the prototype molecules H2, BH, F2, and N2. The complete active space (CAS) part of CASΠDFT accounts for long-range nondynamic correlation, while short-range dynamic correlation is accounted for with the corrected Lee-Yang-Parr correlation functional of density functional theory (DFT). The correction represents the suppression of dynamic correlation with nondynamic correlation, and it is a function of the ratio x(r) between the conditional and conventional densities obtained with the CAS on-top pair density Π(r). For the single-bonded molecules H2, BH, and F2, CASΠDFT succeeds in reproducing the shapes and absolute energies (for H2 and BH) of the benchmark curves, while for the triple-bonded N2 molecule, the addition to CASΠDFT of a multibond correction is required. It accounts for the middle-range dynamic correlation of the same-spin electrons in the (symmetrized) high-spin atomic electron configurations of the dissociating N2.

Decoherence from dipolar interspin interactions in molecular spin qubits

The realization of spin-based logical gates crucially depends on magnetically coupled spin qubits. Thus, understanding decoherence when spin qubits are in close proximity will become a roadblock to overcome. Herein, we propose a method free of fitting parameters to evaluate the qubit phase memory time ${T}_{m}$ in samples with high electron spin concentrations. The method is based on a model aimed to estimate magnetic nuclear decoherence [P. C. E. Stamp and I. S. Tupitsyn, Phys. Rev. B 69, 014401 (2004)]. It is applied to a ground-spin $J=8$ magnetic molecule 1 displaying atomic clock transitions, namely ${{[\mathrm{H}{\mathrm{o}}^{\mathrm{III}}{({\mathrm{W}}_{5}{\mathrm{O}}_{18})}_{2}]}^{9}}^{\ensuremath{-}}$, which remarkably increase ${T}_{m}$ at unusually high electron-spin concentrations. Our approach unveils the causes that limit the coherence reached at the clock transitions in challenging systems such as 1, where recent models fail.

A novel Cs2O–Bi2O3–TiO2–ZnO heterostructure with direct Z-Scheme for efficient photocatalytic water splitting

Efficient production of hydrogen through photocatalytic water splitting requires innovative catalyst design. One of the potential ways to enhance the photocatalyst's efficiency is to prepare metal oxide heterostructures. Herein, we report fabrication of a novel heterostructure consisting of oxides of cesium, bismuth, titanium and zinc (Cs2O–Bi2O3–TiO2–ZnO) by a simple solution combustion method. Diffusion pathway of charge carriers in the as-synthesized Cs2O–Bi2O3–TiO2–ZnO is investigated by high resolution Valence Band X-Ray Photoelectron Spectroscopy (VB-XPS) and electron spin resonance studies. On the basis of analytical findings and redox potential values of each photocatalytic component, a plausible mechanism is proposed showing the formation and diffusion of charge carrier. The results suggest that the charge carrier migration follows the heterojunction approach among TiO2, Bi2O3, and ZnO and the Z-scheme approach between each of them and Cs2O. The performance of the as-obtained catalytic system is investigated by quantifying the photocatalytic formation of oxygen and hydrogen gases, as well as photoelectrochemical water oxidation under simulated sunlight irradiation. In addition, the apparent quantum efficiency is estimated as high as 1.56% at 420 nm. The high apparent quantum efficiency is primarily ascribed to the synergetic effect between Z-scheme and heterojunction operative in the as-prepared heterostructure.