Spin States Research Articles

Modification of the Spin Transition Properties in Hetero‐Anionic Iron(II)‐Triazole Complexes

AbstractThe phenomenon which is called spin crossover is known to occur in some coordination compounds with an octahedral ligand field and electron configurations from 3d4 to 3d7. Thereby, a reversible transition between spin states (high spin and low spin state) is possible, through several external stimuli. Iron(II) triazole complexes exhibit this phenomenon at a wide range of temperatures depending on the ligands and anions used. For this reason, they are often considered for several possible practical applications. It is also possible to combine ligands or anions to modify the transition temperature. The latter of which was rarely discussed in the past. In this study we synthesized a series of iron(II)‐4‐Aminotriazole complexes, with different ratios of chloride‐ and tetrafluoroborate‐anions, of the formula [Fe(Atrz)3]Cl2−X(BF4)X. We show that the combination of these anions leads to transition temperatures between those of their corresponding pure anion complexes. We furthermore present that a simple modification of the synthesis leads to a possible easy way of fine‐tuning transitions temperatures.

Electron-Spin Relaxation in Boron-Doped Graphene Nanoribbons.

Boron-doped graphene nanoribbons are promising platforms for developing organic materials with magnetic properties. Boron dopants can be used to create localized magnetic states in nanoribbons with tunable interactions. Controlling the coherence times of these magnetic states is the very first step in designing materials for quantum computation or information storage. In this work, we address the connection between the relaxation time and the position of the dopants for a series of boron-doped graphene nanofragments. We combine Redfield theory and ab initio calculations of magnetic properties to unveil the mechanism that governs spin relaxation in solution. We demonstrate that relaxation times can be in the order of 1 ms for the selected graphene nanofragments. A detailed analysis of the relaxation mechanism reveals that the spin decoherence is fundamentally driven by fluctuations of the spin-orbit coupling, and the hyperfine interaction facilitated by the thermal motion of the graphene nanofragments. The close connection between relaxation time, hyperfine interaction and the spin-orbit coupling offers the perspective of designing attractive materials with long-lived spin states.

Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li-CO2 Batteries.

Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li-CO2 batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO2 activation. In this study, the local spin states are regulated by incorporating Ni into Co3O4 and its impact on activity in Li-CO2 batteries is explored. The results show that Ni atoms with high spin states in Ni0.1Co2.9O4 facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni0.1Co2.9O4 shows superior catalytic performance with an overpotential of 0.72V and an energy efficiency of ≈70% after 500h. This work provides insights into the relationship between spin states and CO2 reactions, highlighting a promising avenue for developing high-performance metal-CO2 batteries.

Spin-Electrochemistry of Transition Metal Oxides for Energy Storage: Concepts, Advances and Perspectives.

Developing high-capacity and cyclically stable transition metal (TM)-based electrode materials for energy storage devices, such as aqueous ion energy storage systems, is crucial for addressing the growing issue of energy scarcity. The spin state, or spin configuration of the d-electrons, plays a vital role in the electrochemical energy storage performance of these materials. However, there has been a lack of systematic descriptions regarding the role of spin configurations in electrochemical energy storage to date. This review aims to elucidate the advantages of controlling the spin states of metal centers to enhance energy storage performance and highlights recent progress in employing spin state regulation in electrochemical energy storage. Additionally, it covers the various characterization techniques used to determine spin states. Finally, we discuss the future prospects and challenges within this emerging field, with the aim of accelerating the development of spin-based electrochemical energy storage technologies. This review also seeks to provide clear and reliable directions for the design and preparation of novel energy storage materials.

High–Field EPR Studies on Three Binuclear μ–Oxo–Bridged Iron(III) Complexes: Na4[Fe(edta)]2O ⋅ 3H2O, [Fe(phen)2(H2O)]2O(NO3)4 ⋅ 5H2O and [Fe(salen)]2O

AbstractA High–Field, High–Frequency Electron Paramagnetic Resonance (HFEPR) study was performed on the binuclear μ–oxo bridged complexes Na4[Fe(edta)]2O ⋅ 3H2O, [Fe(phen)2(H2O)]2O(NO3)4 ⋅ 5H2O and [Fe(salen)]2O, where edtaH4 = ethylenediaminetetraacetic acid, phen=1,10–phenanthroline and salenH2 is NN′–ethylenebis(salicylideneimine). The spin Hamiltonian parameters were determined for the thermally excited spin states with spin S=1, 2 and 3. The contributions to the zero–field splitting due to the local zero field splitting on individual iron ions and to the anisotropic metal–metal interactions were evaluated. Surprisingly large magnitudes of the anisotropic exchange interactions were found.

Variable structures in the stellar wind of the HMXB Vela X-1

Strong stellar winds are an important feature in wind-accreting high-mass X-ray binary (HMXB) systems. Exploring their structure provides valuable insights into stellar evolution and their influence on surrounding environments. However, the long-term evolution and temporal variability of these wind structures are not fully understood. This work probes the archetypal wind-accreting HMXB Vela X-1 using the Monitor of All-sky X-ray Image (MAXI) instrument to study the orbit-to-orbit absorption variability in the $2–10$ keV energy band across more than 14 years of observations. Additionally, the relationship between hardness ratio trends in different binary orbits and the spin state of the neutron star is investigated. We calculated X-ray hardness ratios to track absorption variability, comparing flux changes across various energy bands, as the effect of absorption on the flux is energy-dependent. We assessed variability by comparing the hardness ratio trends in our sample of binary orbits to the long-term averaged hardness ratio evolution derived from all available MAXI data. Consistent with prior research, the long-term averaged hardness ratio evolution shows a stable pattern. However, the examination of individual binary orbits reveals a different hardness ratio evolution between consecutive orbits with no evident periodicity within the observed time span. We find that fewer than half of the inspected binary orbits align with the long-term averaged hardness evolution. Moreover, neutron star spin-up episodes exhibit more harder-than-average hardness trends compared to spin-down episodes, although their distributions overlap considerably. The long-term averaged hardness ratio dispersion and evolution are consistent with absorption column densities reported in literature from short observations, indicating that a heterogeneous wind structure -- from accretion wakes to individual wind clumps -- likely drives these variations. The variability observed from orbit to orbit suggests that pointed X-ray observations provide limited insights into the overall behaviour of the wind structure. Furthermore, the link between the spin state of the neutron star and the variability in orbit-to-orbit hardness trends highlights the impact of accretion processes on absorption. This connection suggests varying accretion states influenced by fluctuations in stellar wind density.

A Nanosized {NiII18} Cluster with a 'Flying Saucer' Topology Exhibiting Slow Relaxation of Magnetisation Phenomena at Both 15 K and 1.3 K.

A high-nuclearity {Ni18} complex (1) with a unique 'flying saucer' motif has been prepared from the organic chelate, α-methyl-2-pyridine-methanol (mpmH), in conjunction with bridging azido (N3-) and peroxido (O22-) ligands. Magnetic susceptibility measurements revealed the presence of both ferro- and antiferromagnetic exchange interactions between the metal centres in 1, and the stabilization of spin states with appreciable S values at two different temperature regimes. The end-on bridging azido and alkoxido groups are in all likelyhood the ferromagnetic mediators, while the η3:η3:μ6-bridging peroxides most likely promote the antiparallel alignment of the metals' spin vectors, yielding an overall non-zero spin ground state for the centrosymmetric compound 1. Furthermore, the {Ni18} nanosized cluster behaves as a single-molecule magnet, exhibiting magnetic hysteresis at low temperatures and two relaxation processes at 15 K and 1.3 K, a very rare phenomenon in polynuclear magnetic 3d-metal clusters.

Dual Signature of Chirality Induced Spin Selectivity through Spontaneous Resolution of 2D Metal–Organic Frameworks

AbstractThe Chiral‐Induced Spin Selectivity (CISS) effect has emerged as a fascinating phenomenon within the realm of electron's spin manipulation, showcasing a unique interplay between electron's spin and molecular chirality. Subsequent to its discovery, researchers have been actively involved in exploring the new chiral molecules as effective spin filters. In the realm of observing the CISS effect, the conventional approach has mandated the utilization of two distinct enantiomers of chiral molecules. However, this present study represents a significant advancement by demonstrating the ability to control both spin states of electrons in a single system. In this work, we have demonstrated the preparation of chiral metal–organic frameworks (MOFs) via a “spontaneous resolution” process, obviating the requirement for chiral sources. This resulted in the production of chiral crystals exhibiting opposite handedness (1P and 1M) and these crystals were subsequently employed as a new class of spin filters based on CISS effect. Remarkably, this work signifies the first instance of achieving dual signature of spin selectivity from a single and exclusively achiral system through a spontaneous resolution process. This holds immense potential as it facilitates the production of two distinct spin‐filtering materials from a unified system. Furthermore, we investigated the contact potential differences (CPD) of these chiral crystals and, for the first time, associated it with the preferential spin transport properties. Our findings revealed a correlation between the CPD and the chirality of the crystals, as well as the magnetization orientations of the ferromagnetic substrate, which can be elucidated by the CISS effect. In overall, the significant findings achieved using these robust and easily synthesized MOF crystals without the requirement for chiral medium represent a crucial advancement in enhancing the effectiveness of spin filtering materials to produce spintronic devices.

Role of harmonic and anharmonic interactions in controlling the cooperativity of spin-crossover molecular crystals

We present a theoretical model of spin transitions in homogeneous spin-crossover (SCO) materials, based on the description of the interactions between SCO molecules by the Lennard-Jones potential in which the equilibrium distances depend on the spin states of the linked molecules. By expanding the potential to order 3 considering a homogeneous lattice spacing, we demonstrate that the present model is isomorphic with an Ising-like model combining infinite long-range “ferromagnetic-like” interactions, competing with short-range “antiferromagnetic-like” between nearest neighbors in the case of harmonic interactions. When an anharmonic contribution is included, the short-range interaction becomes dependent on the average high-spin fraction, and changes its sign along the spin transition. The thermodynamic properties of the model were first investigated analytically in mean field approximation for both harmonic and anharmonic cases, for which we clarify the conditions for obtaining gradual and first-order transitions. Moreover, we demonstrated that within this approximation, the strength of the antiferromagnetic-like interactions are insufficient to produce multistep transitions. In contrast, the resolution of the previous emerging Ising-like model by Monte Carlo simulations demonstrated the possibility of obtaining gradual, first-order and two-step transitions as a result of the antagonism between long- and short-range interactions. Overall, the obtained results demonstrate the suitability of the present theoretical model to describe cooperative SCO materials. The key message of our paper is that our model can be used to predict complex behavior of spin-crossover crystals. Published by the American Physical Society 2024

Unveiling the spin adaptability of electrocatalytic nitrogen reduction catalyzed by Fe, Ru and Os-anchored nitrogen-doped graphene

It is of a great challenge to achieve efficient single-atom catalysts (SACs) for electrocatalytic nitrogen reduction. Especially, the SACs from transition metals have complex electron conformation. It is urgently necessary to examine the effect of spin state of transition metals on the catalytic performance of SACs for nitrogen fixed. In this work, using density functional theory (DFT) calculations, we firstly evaluated the catalytic capability of 21 transition metals to achieve the most potential metals with the special electron conformation of d6, including Fe, Ru and Os, to construct SACs. Our examinations revealed that the catalytic performance of SAC for nitrogen reduction increases with the decrease of the spin multiplicity for the same metal through the same reaction pathway and further improves with the increase of period number of transition metal. Additionally, the selectivity of SAC for nitrogen reduction reaction also increases with the increase of period over hydrogen evolution reaction under the low spin state. Finally, we found that the OsN4C catalysts had excellent catalytic performance for nitrogen reduction with the extremely low overpotential (0.03V) through the distal reaction path under the low spin state, which were expected to be the potential industrial applications for electrocatalytic nitrogen reduction.

Coherence of NV defects in isotopically enriched 6H-28SiC at ambient conditions

The unique spin-optical properties of NV defects in SiC, coupled with silicon carbide's advanced technology compared to diamond, make them a promising candidate for quantum technology applications. In this study, using photoinduced pulse ESR at 94 GHz (3.4 T), we reveal the room temperature spin coherence of NV defects in 6H-28SiC, purified to reduce 29Si concentration to ≈1%, four times below its natural level. We demonstrate room temperature (300 K) Hahn-echo coherence time T2 = 23.6 μs, spin–lattice relaxation time T1 = 0.1 ms, and coherent control over optically polarized NV spin states through Rabi nutation experiments. We reveal long inhomogeneous dephasing time T2* = 1.5 μs, which is about five times greater than that measured for NV defects in SiC with natural isotopic content. Our observations highlight again the potential of NV defects in 6H-28SiC, which exhibit near-infrared optical excitation and emission properties compatible with O-band fiber optics, as promising candidates for applications in quantum sensing, communication, and computation.

Spin Mixing in Intramolecular Singlet Fission: A First-Principles-Based Quantum Dynamical Study.

We investigate the dynamical interplay between the different triplet-pair spin states that are formed in the intramolecular singlet fission process in a series of pentacene-based dimers covalently bonded to a phenylene linker in ortho, meta, and para positions. Using first-principles calculations and a density matrix quantum dynamical approach we show that the spin dipole-dipole interaction leads to significant population of the quintet spin manifold in these regioisomers when the singlet, triplet and quintet triplet-pair states are quasidegenerate. Furthermore, we also show that the relative arrangement of the pentacene-like moieties has a profound impact on the dynamics of the spin-mixing process, affecting both the relative population of the different spin-states involved in the dynamics and the time scale of the process.

HighSpin-State Modulation of Catalytic Centers by Weak Ligand Field for Promoting Sulfur Redox Reaction in Lithium-Sulfur Batteries.

The spin state of transition-metal compounds in lithium-sulfur batteries (LSBs) significantly impacts the electronic properties and the kinetics of sulfur redox reactions (SRR). However, accurately designing the spin state remains challenging, which is crucial for understanding the structure-performance relationship and developing high-performance electrocatalysts. Herein, the CoF2, specifically the Co2+ with 3d7 electrons in a high-spin state distribution (t2g5eg2), were tailored predictably for the first time through the weak coordination field effect of the F element. Both DFT calculations and experimental results confirm that the spin state of Co2+ transitions from low- to high-spin configurations and strongly interacts with sulfur species through Co-S and Li-F bonds during the SRR process. This interaction weakens the S-S bond, promoting its facile cleavage from both ends while also facilitating the rapid and uniform nucleation of Li2S2/Li2S, thus resulting in LSBs with a capacity of 447.7 mAh g-1 at 10 C rates and stable cycling for 1000 cycles, with an acceptable practical capacity of 585 mAh g-1 at a high sulfur loading mass of 10 mg cm-2. This work achieves rational control of the active Co2+ d electron state through the field effect and enriches the application of spin control to accelerate SRR in LSBs.

Momentum shift and on-shell constructible massive amplitudes

We construct tree-level amplitude for massive particles using on-shell recursion relations based on two classes of momentum shifts: an all-line transverse shift that deforms momentum by its transverse polarization vector, and a massive Britto-Cachazo-Feng-Witten-type shift. We illustrate that these shifts allow us to correctly calculate four-point and five-point amplitudes in massive QED, without an ambiguity associated with the contact terms that may arise from a simple “gluing” of lower-point on-shell amplitudes. We discuss various aspects and applicability of the two shifts, including the large-z behavior and complexity scaling. We show that there exists a “good” all-line transverse shift for all possible little group configurations of the external particles, which can be extended to a broader class of theories with massive particles such as massive QCD and theories with massive spin-1 particles. The massive Britto-Cachazo-Feng-Witten-type shift enjoys more simplicity, but a “good” shift does not exist for all the spin states due to the specific choice of spin axis. Published by the American Physical Society 2024

Mechanisms for the Spin-State Switching of Strapped Ni-Porphyrin Complexes Deposited on Metal Surfaces: Insights from Quantum Chemical Calculations.

The incorporation of molecular switches on nanodevices requires both the intactness of the molecule once deposited on a substrate and the persistence of the reversible switching feature. Recently, the reversible spin-switching of strapped Ni(II)-porphyrin complexes deposited on Ag(111) surface is demonstrated with low-temperature scanning tunneling microscopy (STM). The spin transition is accompanied by the coordination change of the metal center, a phenomenon denominated in coordination-induced spin-state switching (CISSS). In this contribution, the spin switching of the deposited strapped Ni-porphyrin molecules using different quantum chemistry approaches is explored. This calculations inform about the geometry and electronic structure of the adsorbed molecules and the origin of the voltage-dependent switching promoted by the STM tip. Two different mechanisms are inspected to elucidate the key role of the tip, mainly the electron injection between the tip and the molecule and the differential stabilization of the two spin states by the applied electric field between the tip and the silver surface. This study puts in evidence the relevance of the pyridine ligand contained in the strap in the transport properties as in the CISSS process itself.

The edge states of one-dimensional spin-$\frac{1}{2}$-like noninteracting periodic systems under the most compactly supported Wannier-type functions

Abstract A hallmark of topological insulators is topologically protected edge states, which are determined by topological invariants defined under Bloch functions. Of course, not all edge states are stable, and they are independent of topological invariants. And in a recent study, it was found that even stable protected gapless edge states cannot be explained by topological invariants in two-dimensional (2D) systems. Motivated by this idea, we carried out a thorough study in one-dimensional (1D) spin-$\frac{1}{2}$-like noninteracting periodic systems and found that all edge states can be explained by the most compactly supported Wannier-type functions (MCWTFs). All the answers are contained in the flat-band Hamiltonian defined by MCWTFs. Edge states can be obtained by solving special equations using the parameters of MCWTFs. Symmetries are the special solutions of these equations, and we have proved the relationship between zero-energy edge states and symmetry analytically in partial cases, which was only a well-known result in the past. By solving the equations, we also find that not all zero-energy edge states are determined by symmetry, which is beyond the current framework. Through numerical verification, we show that these zero-energy edge states, like those protected by symmetry, are not affected by the energy spectrum of the system, so they are only related to the Bloch functions. We also derive special properties of zero-energy edge states protected by chiral symmetry from the perspective of MCWTFs, which are consistent with the previous literature. Finally, we do a test in the 2D case and find the connection between the Chern number and the Wannier functions. Our results show that compared with topological invariants, the origin of the edge state can be understood more comprehensively from the perspective of Wannier functions.

Evolution of metallicity, enhancement of [formula omitted] and magnetic anisotropy energy in Y[formula omitted]NiIrO[formula omitted]: Hydrostatic ([111]) strain influence

Ir-based double perovskite oxides (DPO) provide a distinct electronic and magnetic behavior due to entanglement among lattice distortion, strong electron correlation, and spin–orbit coupling (SOC). In this work, we investigated the hydrostatic ([111]) strain impact on the physical properties of the Y2NiIrO6 DPO using ab-initio calculations. Unstrained motif displayed the ferrimagnetic (FiM) spin state owing to strong antiferromagnetic (AFM) interactions between Ni↑ and Ir↓ ions, further confirmed by the computed partial spin magnetic moments and 3D spin-magnetization density iso-surfaces plots. A Mott-insulating state is established with an energy band gap (Eg) of 0.43 eV due to the existence of a rare Ir+4 state having Jeff.=12 and a Curie temperature (TC) of 198 K using the Heisenberg Hamiltonian model, which is up to the experimental observations. The easy magnetic axis is the [010] (b-axis) having a giant magnetic anisotropy energy (MAE) constant of 1.7 × 108 erg/cm3. Moreover, it is predicted that strain holds the FiM spin order as a magnetic ground state for the considered range of ±8%. Notably, an electronic transition from Mott-insulating to a metallic state is established at a critical compressive strain of −8%, where the admixture of Ir 5d states appears at/around the Fermi level. On the other hand, Eg solely increases with the increase of tensile strain amplitude. Due to strong and weak hybridization, the spin/orbital magnetic moment value is reduced and enhanced as a function of compressive and tensile strains, respectively. Along with this, it is found that MAE/TC increases to 25%/18% and 15%/10% at −8% compressive and ＋8% tensile strains due to larger structural distortion than that of the unstrained one, which enhances the system potential for magnetic memory devices.

Activating the Mn Single Atomic Center for an Efficient Actual Active Site of the Oxygen Reduction Reaction by Spin-State Regulation.

The ligand engineering for single-atom catalysts (SACs) is considered a cutting-edge strategy to tailor their electrocatalytic activity. However, the fundamental reasons underlying the reaction mechanism and the contemplation for which the actual active site for the catalytic reaction depends on the pyrrolic and pyridinic N ligand structure remain to be fully understood. Herein, we first reveal the relationship between the oxygen reduction reaction (ORR) activity and the N ligand structure for the manganese (Mn) single atomic site by the precisely regulated pyrrolic and pyridinic N4 coordination environment. Experimental and theoretical analyses reveal that the long Mn-N distance in Mn-pyrrolic N4 enables a high spin state of the Mn center, which is beneficial to reduce the adsorption strength of oxygen intermediates by the high filling state in antibond orbitals, thereby activating the Mn single atomic site to achieve a half-wave potential of 0.896 V vs RHE with outstanding stability in acidic media. This work provides a new fundamental insight into understanding the ORR catalytic origin of Mn SACs and the rational design strategy of SACs for various electrocatalytic reactions.

Covariant Representation of Spin and Entanglement—A Review and Reformulation

A consistent theory of quantum entanglement requires that constituent single-particle states belong to the same Hilbert space, the coherent eigenstates of a complete set of operators in a given representation, defined with respect to a shared continuous parameterization. Formulating such eigenstates for a single relativistic particle with spin, and applying them to the description of many-body states, presents well-known challenges. In this paper, we review the covariant theory of relativistic spin and entanglement in a framework first proposed by Stueckelberg and developed by Horwitz, Piron, et al. This approach modifies Wigner’s method by introducing an arbitrary timelike unit vector nμ and then inducing a representation of SL(2,C), based on pμ rather than on the spacetime momentum. Generalizing this approach, we construct relativistic spin states on an extended phase space {(xμ,pμ),(ζμ,πμ)}, inducing a representation on the momentum πμ, thus providing a novel dynamical interpretation of the timelike unit vector nμ=πμ/M. Studying the unitary representations of the Poincaré group on the extended phase space allows us to define basis quantities for quantum states and develop the gauge invariant electromagnetic Hamiltonian in classical and quantum mechanics. We write plane wave solutions for free particles and construct stable singlet states, and relate these to experiments involving temporal interference, analogous to the spatial interference known from double slit experiments.

Tuning the quantum spin states of Co-phthalocyanine on good, semi-, and half-metals

Tuning the quantum spin states of Co-phthalocyanine on good, semi-, and half-metals