Spin-orbit Coupling Research Articles

The Chemical Bond at the Bottom of the Periodic Table: The Case of the Heavy Astatine and the Super-Heavy Tennessine.

In this work, we study the chemical bond in molecules containing heavy and super-heavy elements according to the current state-of-the-art bonding models. An Energy Decomposition Analysis in combination with Natural Orbital for Chemical Valence (EDA-NOCV) within the relativistic four-component Dirac-Kohn-Sham (DKS) framework is employed, which allows to successfully include the spin-orbit coupling (SOC) effects on the chemical bond description. Simple halogen-bonded adducts ClX⋯L (X=At, Ts; L=NH3, Br-, H2O, CO) of astatine and tennessine have been selected to assess a trend on descending along a group, while modulating the ClX⋯L bond features through the different electronic nature of the ligand L. Interesting effects caused by SOC have been revealed: i) a huge increase of the ClTs dipole moment (which is almost twice as that of ClAt), ii) a lowering of the ClX⋯L bonding energy arising from different contributions to the ClX…L interaction energy strongly depending on the nature of L, iii) a quenching of one of the π back-donation components to the bond. In the ClTs(CO) adduct, the back-donation from ClTs to CO becomes the most important component. The analysis of the electronic structure of the ClX dimers allows for a clear interpretation of the SOC effects in these systems.

Doping dependence of spin-momentum locking in bismuth-based high-temperature cuprate superconductors

Non-zero spin orbit coupling has been reported in several unconventional superconductors due to the absence of inversion symmetry breaking. This contrasts with cuprate superconductors, where such interaction has been neglected for a long time. The recent report of a non-trivial spin orbit coupling in overdoped Bi2212 cuprate superconductor, has re-opened an old debate on both the source and role of such interaction and its evolution throughout the superconducting dome. Using high-resolution spin- and angle-resolved photoemission spectroscopy, we reveal a momentum-dependent spin texture throughout the hole-doped side of the superconducting phase diagram for single- and double-layer bismuth-based cuprates. The universality of the reported effect among different dopings and the disappearance of spin polarization upon lead substitution, suggest a common source. We argue that local structural fluctuations of the CuO planes and the resulting charge imbalance may cause local inversion symmetry breaking and spin polarization, which might be crucial for understanding cuprates physics.

An Earth Encounter as the Cause of Chaotic Dynamics in Binary Asteroid (35107) 1991VH

Among binary asteroids, (35107) 1991VH stands out as unique given the likely chaotic rotation within its secondary component. The source of this excited dynamical state is unknown. In this work, we demonstrate that a past close encounter with Earth could have provided the necessary perturbation to allow the natural internal dynamics, characterized by spin–orbit coupling, to evolve the system into its current dynamical state. In this hypothesis, the secondary of 1991VH was previously in a classical 1:1 spin–orbit resonance with an orbit period likely between 28 and 35 hr before being perturbed by an Earth encounter within ∼80,000 km. We find that if the energy dissipation within the secondary is relatively inefficient, this excited dynamical state could persist to today and produce the observed ground-based measurements. Coupled with the orbital history of 1991VH, we can then place a constraint on the tidal dissipation parameters of the secondary.

Dirac crossings and band inversion in hexagonal superconductors emerging by chemical substitution: SrAlGe, BaAlGe, SrGaGe and BaGaGe

In this work, we used DFT calculations to compare the electronic structure of four hexagonal superconducting materials. Two of them are SrAlGe and BaAlGe, and the other two are given by substituting Al for Ga, resulting in SrGaGe and BaGaGe. The band structure, the density of states, and the Fermi surface were obtained for each compound with and without the spin–orbit coupling effect. For the SrGaGe and BaGaGe compounds, a band unfolding calculation was performed. We found that BaGaGe exhibits a quasi-flat-band localized in a specific direction of the Brillouin zone. In addition, band inversion can be induced by replacing Al for Ga in these compounds. Furthermore, we found that linear band crossings are gaped after spin–orbit coupling is considered to SrAlGe, BaAlGe, SrGaGe, and BaGaGe. These Dirac-like band crossings point to non-trivial topological behavior.

Temperature Dependence of the Electronic Structure of TlInSe2 and Spin–Orbit Coupling

Temperature Dependence of the Electronic Structure of TlInSe₂ and Spin–Orbit Coupling

Exact ground states for pentagon chains with spin–orbit interaction

Exact ground states (GS) are deduced for conducting polymers possessing pentagon type of unit cell. The study is done in the presence of many-body spin–orbit interaction (SOI), local and nearest-neighbor Coulomb repulsion (CR), and presence of external E electric and B magnetic fields (EF). The simultaneous presence of SOI, CR, and EF in the exact conducting polymer GS is a novelty, so the development of the technique for the treatment possibility of such strongly correlated cases is presented in detail. The deduced GS show a broad spectrum of physical characteristics ranging from charge density waves doubling the system periodicity, metal–insulator transitions, to interesting external field-driven effects as, e.g., modification possibility of a static charge distribution by a static EF.Graphic abstract

Spectroscopic and computational characterization of lanthanide-mediated bond activation of ethylamine

Ln (Ln = La and Ce) atom reactions with ethylamine are conducted in a pulsed laser vaporization supersonic molecular beam source. Dehydrogenation and association metal-containing species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln ethylimido species in the formula Ln(NC2H5) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling through multiconfiguration quasi-degenerate second-order perturbation theory for the Ce species. The MATI spectrum of lanthanum ethylimido La(NCH2CH3) has a single vibronic band system from the ionization of the doublet ground state with the La 6s1 configuration, whereas that of the cerium ethylimido Ce(NCH2CH3) displays two vibronic band system from the ionization of the two lowest-energy spin-orbit coupling states with the Ce 4f16s1 configuration. Both Ln ethylimido complexes are formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group. Two additional isomers of Ln(NC2H5) include a four-membered metallacycle Ln(NHCH2CH2) from the dehydrogenation of the amino and methyl groups and a three-membered cycle Ln(NHCHCH3) from the dehydrogenation of the amino and methylene groups. The cyclic isomers are not observed experimentally as they are not populated under the experimental conditions.

Tailoring magnetic properties of novel (La0.25Nd0.25Sm0.25Gd0.25)1-xHoxMnO3 high-entropy perovskite ceramics by Ho doping

High-entropy perovskite ceramics (HEPCs) with equal atomic ratios have recently emerged as a highly promising class of materials due to their unique magnetic properties. However, the crystal structure, microstructure and magnetic properties of unequal atomic ratios HEPCs have yet to be fully investigated. In this paper, single-phase HEPCs (La0.25Nd0.25Sm0.25Gd0.25)1-xHoxMnO3 ((LNSG)1-xHxMO) have been synthesized using solid-state reactions. The effect of Ho element content (x = 0.25, 0.3, 0.35 and 0.4) on the structure and magnetic properties was systematically investigated. All samples exhibit an orthorhombic perovskite structure with a Pbnm space group and show obvious crystallization characteristics after sintering at 1250 °C for 16 h (LNSG)1-xHxMO HEPCs display a smooth surface texture and distinct grain boundaries, as well as significant hysteresis effects at T = 5 K. The spin-orbit interaction and magnetic anisotropy between Ho and Mn ions increase with the increase of Ho content, which increases the saturation magnetization (Ms) of HEPCs. (LNSG)0.6H0.4MO exhibits the lowest magnetic hysteresis losses among the considered samples, attributed to its highest Ms (50.95 emu/g) and the lowest coercivity Hc (0.6 kOe). These characteristics endow it with a potential application in magnetic storage devices.

Josephson tunneling controlled by spin-orbit interaction

On the occasion of the 50th anniversary of point-contact spectroscopy, we review and extend some of our recent studies on the effects of spin-orbit interactions located at an electric point contact connecting two bulk superconductors. In particular, we study the effects on the Josephson tunneling of Cooper pairs between the superconductors. We demonstrate that such tunneling forces the electronic spin to fluctuate quantum mechanically, transforming a BCS condensate into a quantum superposition of singlet and triplet pairs. The relative prevalence of those pairs can be controlled electrostatically and mechanically. The singlet pairs contribute to the Josephson charge current flowing through the point contact but not to the Josephson spin current injected into the superconductors. The spin-polarized pairs contribute to the injected Josephson spin current but not to the superconducting charge flow. These results allow for new functionalities of spin-active Josephson junctions.

Magnetic instability in the spin susceptibility of chiral carbon-based structures

Chiral carbon nanostructures have been found to display unexpected magnetic behaviors. Several theoretical calculations performed in the macroscopic limit q=0 have addressed or predicted some of these findings. To gain more insight into the magnetism of these systems at finite q, here we use linear response theory to calculate the wave-vector-dependent spin susceptibility χ(q,0) in a half-filling tight-binding model of a helix of carbon atoms with intrinsic spin-orbit coupling (SOC). We find that at the nesting wave number q=2kF the paramagnetic state of the system is unstable with respect to the formation of a spin-density-wave type state. Chirality has a small effect on the paramagnetic phase but has no impact on the spin-density-wave type state. Published by the American Physical Society 2024

Photo-induced non-collinear interlayer RKKY coupling in bulk Rashba semiconductors

The interplay between light-matter, spin-orbit, and magnetic interactions allows the investigation of light-induced magnetic phenomena that are otherwise absent without irradiation. We present our analysis of light-driven effects on the interlayer exchange coupling mediated by a bulk Rashba semiconductor in a magnetic multilayer. The collinear magnetic exchange coupling mediated by the photon-dressed spin-orbit coupled electrons of BiTeI develops light-induced oscillation periods and displays new decay power laws, both of which are enhanced with an increasing light-matter coupling. For magnetic layers with non-collinear magnetization, we find a non-collinear magnetic exchange coupling uniquely generated by light-driving of the multilayer. As the non-collinear magnetic exchange coupling mediated by the photon-dressed electrons of BiTeI is unique to the irradiated system and it is enhanced with increasing light-matter coupling, this effect offers a promising platform of investigation of light-driven effects on magnetic phenomena in spin-orbit coupled systems. In this platform, light properties, such as its intensity, can serve as external knobs for inducing non-collinear couplings of the interlayer exchange and for modulating the collinear couplings. Both of these effects signify the photo-generated modification in the spin textures of spin-orbit coupled electrons in BiTeI.

First-principles study of electronic and magnetic properties of Fe atoms on Cu2N/Cu(100)

Abstract First-principles calculations were conducted to investigate the structural, electronic, and magnetic properties of single Fe atoms and Fe dimers on Cu2N/Cu(100). Upon adsorption of an Fe atom onto Cu2N/Cu(100), robust Fe–N bonds form, resulting in the incorporation of both single Fe atoms and Fe dimers within the surface Cu2N layer. The partial occupancy of Fe-3d orbitals lead to large spin moments on the Fe atoms. Interestingly, both single Fe atoms and Fe dimers exhibit in-plane magnetic anisotropy, with the magnetic anisotropy energy (MAE) of an Fe dimer exceeding twice that of a single Fe atom. This magnetic anisotropy can be attributed to the predominant contribution of the component along the x direction of the spin–orbital coupling Hamiltonian. Additionally, the formation of Fe–Cu dimers may further boost the magnetic anisotropy, as the energy levels of the Fe-3d orbitals are remarkably influenced by the presence of Cu atoms. Our study manifests the significance of uncovering the origin of magnetic anisotropy in engineering the magnetic properties of magnetic nanostructures.

Room temperature chiral magnetoresistance in a chiral-perovskite-based perpendicular spin valve

Chirality-induced spin selectivity (CISS) allows for the generation of spin currents without the need for ferromagnets or external magnetic fields, enabling innovative spintronic device designs. One example is a chiral spin valve composed of ferromagnetic and chiral materials, in which the resistance depends on both the magnetization direction of the ferromagnet and the chirality of the chiral material. So far, chiral spin valves have predominately employed chiral organic molecules, which have limited device applications. Chiral perovskites, which combine the properties of inorganic perovskites with chiral organic molecules, provide an excellent platform for exploring CISS-based devices. However, previous chiral perovskite-based spin valves exhibited magnetoresistance (MR) only at low temperatures. Here, we report room temperature MR in a chiral spin valve consisting of chiral perovskites/AlOx/perpendicular ferromagnet structures. It is observed that the chiral MR increases with rising temperature, suggesting the crucial role of phonon-induced enhancement of spin–orbit coupling in CISS in our device. Furthermore, we enhanced the chiral MR by introducing chiral molecules with amplified chirality. This highlights the potential of chirality engineering to improve CISS and the associated chiral MR, thereby opening possibilities for chiral spin valves tailored for cutting-edge spintronic applications.

Theoretical investigation into potential thermoelectric material Monolayer InI with direct bandgap and ultralow lattice thermal conductivity

Monolayer metal iodides are garnering widespread attention due to their ultralow lattice thermal conductivity and their potential applications in the field of thermoelectrics. Here, we utilized first-principles calculations and Boltzmann transport theory to thoroughly investigate the thermoelectric behavior of monolayer InI. Results indicate that this material functions as a direct bandgap semiconductor and features an exceptionally low lattice thermal conductivity of 0.27 W m−1K−1 at 300 K, a result of its low group velocities and short phonon lifetimes. Furthermore, transport coefficients were calculated with enhanced precision through the Wannier interpolation method, incorporating the HSE06 hybrid functional and spin-orbit coupling (SOC) effects. Remarkably, the maximum thermoelectric figure of merit (ZT) values for monolayer InI demonstrate substantial growth with increased temperatures, surging from 0.31 at 300 K to 1.20 at 450 K for p-type, and escalating from 0.26 at 300 K to 0.72 at 450 K for n-type. These promising low-temperature thermoelectric properties exhibited by monolayer InI suggest its suitability for integration into the production of thermoelectric devices.

Valley-Dependent Electronic Properties of Metal Monochalcogenides GaX and Janus Ga2XY (X, Y = S, Se, and Te).

Two-dimensional (2D) materials have shown outstanding potential for new devices based on their interesting electrical properties beyond conventional 3D materials. In recent years, new concepts such as the valley degree of freedom have been studied to develop valleytronics in hexagonal lattice 2D materials. We investigated the valley degree of freedom of GaX and Janus GaXY (X, Y = S, Se, Te). By considering the spin-orbit coupling (SOC) effect in the band structure calculations, we identified the Rashba-type spin splitting in band structures of Janus Ga2SSe and Ga2STe. Further, we confirmed that the Zeeman-type spin splitting at the K and K' valleys of GaX and Janus Ga2XY show opposite spin contributions. We also calculated the Berry curvatures of GaX and Janus GaXY. In this study, we find that GaX and Janus Ga2XY have a similar magnitude of Berry curvatures, while having opposite signs at the K and K' points. In particular, GaTe and Ga2SeTe have relatively larger Berry curvatures of about 3.98 Å2 and 3.41 Å2, respectively, than other GaX and Janus Ga2XY.

Relativistic Effects in Ligand Field Theory (I): Optical Properties of d1 Atoms in Oh' Symmetry.

Ligand field theory, which explains the splitting of degenerate nd atomic orbitals due to static electric fields from point-charge ligands, is rederived using Dirac orbitals instead of Schrödinger orbitals, specifically using the nd3/2 and nd5/2 spinors. This formalism is, to some extent, equivalent to incorporating the spin-orbit interaction either in the nd atomic orbitals or in the ligand field orbitals (e.g., the t2g and eg orbitals arising from Oh symmetry). The spin-orbit interaction is of fundamental importance in the description of the magnetic and optical properties of the 4d and 5d transition metal complexes. Algebraic equations for the relativistic energy levels of d1 octahedral complexes as functions of the spin-orbit coupling constant ξnd and the ligand field parameters Dq and Dp are derived. It is demonstrated that these parameters allow a direct link between the ligand field theory and ab initio relativistic calculations, consistent with the emerging ab initio ligand field theory. The spin-orbit coupling constant and ligand field parameters of ReF6 obtained from optical absorption spectra are carefuly in the light of the new theory.

Producing sustainable flame-retardant room temperature phosphorescent materials from natural wood assisted by borax

Materials exhibiting room temperature phosphorescence (RTP) and flame-retardant properties show great potential in a wide range of applications. However, such materials were rarely reported. Here, we found that the RTP of lignin is activated by borax. This is because borax forms non-covalent interaction with lignin, enhancing the spin-orbit coupling (SOC) and restricting the vibration of lignin. Encouraged by this result, borax was introduced into a wood matrix (B-wood) to activate the RTP of naturally occurring lignin in a wood matrix with a lifetime of ∼263.1 ms. Moreover, B-wood displays V-0-level flame retardant properties, the highest level in UL-94 standard (typical standard in evaluating flame retardant properties). As a demonstration of potential applications, B-wood was processed into multifunctional wooden materials and films, which simultaneously exhibit flame retardant properties and generate RTP emission.

Strain-Amplified Exciton Chirality in Organic-Inorganic Hybrid Materials.

Chiral organic-inorganic hybrids combining chirality of organic molecules and semiconducting properties of inorganic frameworks generate chiral excitons without external spin injection, creating the potential for chiroptoelectronics. However, the relationship between molecular chirality and exciton chirality is still unclear. Here we show the strain-amplified exciton chirality in one-dimensional chiral metal halides. Utilizing chirality-induced spin-orbital coupling theory, we quantitatively demonstrate the impact of the strain-engineered molecular assembly of chiral cations on exciton chirality, offering a feasible way to amplify exciton chirality by molecular manipulation.

Rydberg-Induced Topological Solitons in Three-Dimensional Rotation Spin–Orbit-Coupled Bose–Einstein Condensates

Abstract We introduce a novel approach for generating stable three-dimensional (3D) spatiotemporal solitons (SSs) within a rotating Bose-Einstein Condensates, incorporating Spin-Orbit-Coupling (SOC), a weakly anharmonic potential and cold Rydberg atoms. This intricate system facilitates the emergence of quasi-stable 3D SSs with topological charges |m| ≤ 3 in two spinor components, potentially exhibiting diverse spatial configurations. Our findings reveal that the Rydberg long-range interaction, spin-orbit coupling, and rotational angular frequency exert significant influence on the domains of existence and stability of these solitons. Notably, the Rydberg interaction contributes to a reduction in the norm of topological solitons, while the SOC plays a key role in stabilizing the SSs with finite topological charges. This research of SSs exhibit potential applications in precision measurement, quantum information processing, and other advanced technologies.

Impact of symmetry breaking and spin-orbit coupling on the band gap of halide perovskites

Impact of symmetry breaking and spin-orbit coupling on the band gap of halide perovskites