Spin-orbit Coupling Research Articles

Achieving Sub‐ppm Sensitivity in SO2 Detection with a Chemically Stable Covalent Organic Framework

AbstractWe report the inaugural experimental investigation of covalent organic frameworks (COFs) to address the formidable challenge of SO2 detection. Specifically, an imine‐functionalized COF (SonoCOF‐9) demonstrated a modest and reversible SO2 sorption of 3.5 mmol g−1 at 1 bar and 298 K. At 0.1 bar (and 298 K), the total SO2 uptake reached 0.91 mmol g−1 with excellent reversibility for at least 50 adsorption‐desorption cycles. An isosteric enthalpy of adsorption (ΔHads) for SO2 equaled −42.3 kJ mol−1, indicating a relatively strong interaction of SO2 molecules with the COF material. Also, molecular dynamics simulations and Møller–Plesset perturbation theory calculations showed the interaction of SO2 with π density of the rings and lone pairs of the N atoms of SonoCOF‐9. The combination of experimental data and theoretical calculations corroborated the potential use of this COF for the selective detection and sensing of SO2 at the sub‐ppm level (0.0064 ppm of SO2).

Halogen Impact on the Supramolecular Organization of Chiral Phthalimide Emitters Displaying Room Temperature Phosphorescence.

Room temperature phosphorescence from organic materials has attracted an increasing attention in the recent years due to their potential application in various advancing technologies, notably in bioimaging and displays. In this context, heavy atoms such as halogen ones revealed useful tools to enhance the spin-orbit coupling (SOC) of molecular organic phosphors. However, the effect of halogen at the supramolecular level remains less understood, especially in the field of molecular crystals where additional factors can impact the phosphorescence emission. Here, we investigate external effect of halogens on the phosphorescence of chiral phthalimides molecular crystals. The results show that changing the nature of the halogen atom onto the phthalimide core leads to an evolution of the photophysical properties of the materials which does not necessarily follow the classical trend imposed by the expected internal heavy atom effect. Beyond this aspect, we showed that the halogen atom has a profound impact on the packing between the chromophores at the supramolecular level which is of paramount importance towards the optical properties (PLQY and lifetimes) of the different phosphors examined.

Phase diagrams and topological mixed edge states in silicene with intrinsic and extrinsic Rashba effects

We investigate the topological phases and corresponding edge states in silicene with fixed intrinsic and extrinsic Rashba spin-orbit couplings. The results show that silicene can exhibit four distinct topological phases, such as two types of valley-polarized quantum anomalous Hall effect (QAHE) and two types of QAHE that can be effectively controlled by the exchange field and electric field. In addition, these topological phases only correspond to the valley edge states distributed at the boundary of silicene. In particular, when the off-resonant circularly polarized (ORCP) light is further considered, silicene can host richer topological phases that are characterized by the Chern numbers from C=−3 to C=3, where the corresponding mixed edge states—where the valley and nonvalley edge states could coexist—can remarkably appear. More interestingly, the special higher Chern numbers C=±3 determine two valley edge states and one nonvalley edge state, with the right-moving or left-moving direction. These peculiar edge states are attributed to the ORCP light destroying the collapse of the Dirac cones that the valley edge states bridge. Additionally, silicene can experience multiple edge-state transitions for identical Chern numbers C=±2 between the valley edge state, nonvalley edge state, and two types of mixed edge state, under the ORCP light. This work may provide a platform and point of view for investigating other forms of topological edge state and is beneficial for designing multifunctional topological devices. Published by the American Physical Society 2024

Chirality reversal quantum phase transition in flat-band topological insulators.

Quantum anomalous Hall effect generates dissipationless chiral conductive edge states in materials with large spin-orbit coupling and strong, intrinsic, or proximity magnetization. The topological indexes of the energy bands are robust to smooth variations in the relevant parameters. Topological quantum phase transitions between states with different Chern numbers require the closing of the bulk bandgap: C=1→C=1/2 corresponds to the transition from a topological insulator to gapless in k=0 state- quantum anomalous semimetal. Within the Bernevig-Hughes-Zhang model of 2D topological quantum well, this study identifies another type of topological phase transition induced by a magnetic field. The transition C=±1→C=∓1occurs when the monotonic Zeeman field reaches the threshold value and thus triggers the reversal of edge modes chirality. The calculated threshold depends on the width of the conduction and valence bands and is more experimentally achievable the flatter the bands. The effect of the topological phase transition ∆C=2 can be observed experimentally as a jump in magnetoresistance.&#xD.

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.

Slow Magnetic Relaxation in a Californium Complex.

We report the synthesis and characterization of the macrocyclic californium derivative Na[Cf(H2O)(DOTA)] (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), 1-Cf, which was studied in comparison to its dysprosium counterpart, Na[Dy(H2O)(DOTA)], 1-Dy. Divergent spectroscopic and magnetic behaviors were observed between 1-Cf and 1-Dy. Based upon spectroscopic measurements, we propose that accessible 5f → 6d transitions (potentially operating in tandem with charge-transfer transitions) are the major contributors to the observed broadband photoluminescence in 1-Cf. Dc magnetic susceptibility data for 1-Cf revealed lower magnetic moments than those previously observed for 1-Dy and expected for an f9 free ion, which calculations suggest is the result of greater ligand field effects. Notably, 1-Cf displays slow magnetic relaxation on the time scale of ac susceptibility measurements, making it the first example of a californium-based single-molecule magnet. A side-by-side comparison of the ac susceptibility data reveals magnetic relaxation properties that widely differ between 1-Cf and 1-Dy. This divergent relaxation behavior is attributed mainly to the inherent difference in spin-orbit coupling between Dy3+ and Cf3+.

Covalent Stabilization of the Iridium-Containing Oxyhydrides Sr2Mn0.5Ir0.5O3.25H0.75 and Sr2Mn0.5Ir0.5O2.66H1.33.

Reaction between Sr2Mn0.5Ir0.5O4 and CaH2 or LiH yields the iridium-containing oxyhydride phases Sr2Mn0.5Ir0.5O3.25H0.75 or Sr2Mn0.5Ir0.5O2.66H1.33, respectively. Analysis of Mn K-edge XANES data indicate the presence of Ir3+ centers in these oxyhydride phases, whose low-spin d6 configuration is consistent with the "covalent stabilization" of the metastable oxyhydride phases, as seen previously in analogous ruthenium and rhodium containing materials. Neutron powder diffraction data indicate the hydride ions are located exclusively within the "equatorial" anion sites of Sr2Mn0.5Ir0.5O3.25H0.75. In contrast, hydride ions are observed on both the equatorial and axial anion sites of Sr2Mn0.5Ir0.5O2.66H1.33. This highly unusual anion distribution is attributed to a combination of the strong trans-influence of Ir-H σ-bonds and the stabilization of fac-IrO3H3 centers by spin-orbit coupling effects. Magnetization data indicate that Sr2Mn0.5Ir0.5O4 and Sr2Mn0.5Ir0.5O3.25H0.75 adopt spin glass states at low temperature, behavior which is attributable to the cation disorder in Sr2Mn0.5Ir0.5O4 and the cation and anion disorder in Sr2Mn0.5Ir0.5O3.25H0.75. In contrast, magnetization data collected from Sr2Mn0.5Ir0.5O2.66H1.33 show no evidence of any magnetic phase transition down to 5 K, consistent with the dilution of the magnetic network by the introduction of diamagnetic Ir3+ on the formation of the oxyhydride phase.

Emerging Anomalous Hall Effect in (111)‐Oriented Artificial Iridate Honeycomb Lattices

AbstractComplex Ir oxides provide a promising platform for investigating cooperativity and competition between Mott physics and spin‐orbit coupling in condensed matter physics. These materials have the potential to reveal intriguing phases, such as topological phases and the Kitaev spin liquid state, an exactly solvable S = 1/2 spin model describing Ir4+ ions on a 2D honeycomb lattice. However, experimental confirmation of such phases in iridate films has been hindered by the difficulty of preparing (111)‐oriented samples of the perovskite phase. Herein, by constructing SrIrO3/SrTiO3 superlattices on SrTiO3 (111) substrates, (111)‐oriented perovskite phase SrIrO3 films are achieved with the unprecedentedly large thickness of 6 unit cells. Electrical and magnetic characterizations reveal that these films exhibit anomalous Hall insulating behavior, significant charge fluctuations, and long‐range antiferromagnetic order. Moreover, these properties can be tuned by varying the thickness of the SrIrO₃ layer. These emergent phenomena underscore the complex interactions among spin‐orbit coupling, electron–electron correlations, and crystal structure in (111)‐oriented artificial iridate honeycomb lattices. Further, spin fractionalization and topological quantum spin liquid may be achieved by tuning the spin–orbit coupling and crystal field intensity from interface engineering.

Spin-valley locked topological phase transitions in reversible strain-tailoring honeycomb motifs

Using an effective low-energy k·p model on the frontier px,y orbitals, we establish a general phase diagram of spin-valley locked band inversion by introducing a mechanical strain field into nonmagnetic honeycomb motifs with robust spin–orbit coupling and intrinsically broken inversion symmetry. Using first-principles calculations, we realize such multiple topological phase transitions in a strained InTe monolayer within experimental reach with the Weyl semimetal as the nontrivial boundary state at two critical strains. The massless Weyl fermions endow the spin and valley Hall effects with ultrafast and dissipationless transport over a broad low-energy window. The valley selective circular dichroism can be regulated by strain-induced band inversion. A crossover between the topologically trivial and nontrivial regimes with sizable bandgaps makes InTe suitable for room-temperature (RT) topological strain-effect transistors. Our work not only demonstrates a fundamental mechanism for exploring tunable topological states and valley physics but also provides a potential platform for realizing many exotic phenomena and RT quantum devices.

Self-consistent quasiparticle GW and hybrid functional calculations for Al/InAs/Al heterojunctions: Band offset and spin-orbit coupling effects

The electronic structure of surfaces and interfaces plays a key role in the properties of quantum devices. Here, we study the electronic structure of realistic Al/InAs/Al heterojunctions using a combination of density functional theory with hybrid functionals and state-of-the-art quasiparticle GW (QSGW) calculations. We find a good agreement between QSGW calculations and hybrid functional calculations, which themselves compare favorably well with angle-resolved photoemission spectroscopy experiments. Our paper confirms the need for well-controlled quality of the interfaces to obtain the needed properties of InAs/Al heterojunctions. A detailed analysis of the effects of spin-orbit coupling on the spin splitting of the electronic states shows a linear scaling in k space, related to the two-dimensional nature of some interface states. The good agreement by QSGW and hybrid functional calculations opens the door towards trustable use of an effective approximation to QSGW for studying very large heterojunctions. Published by the American Physical Society 2024

Highly Accurate and Robust Constraint-Based Orbital-Optimized Core Excitations.

We adapt our recently developed constraint-based orbital-optimized excited-state method (COOX) for the computation of core excitations. COOX is a constrained density functional theory (cDFT) approach based on excitation amplitudes from linear-response time-dependent DFT (LR-TDDFT), and has been shown to provide accurate excitation energies and excited-state properties for valence excitations within a spin-restricted formalism. To extend COOX to core-excited states, we introduce a spin-unrestricted variant which allows us to obtain orbital-optimized core excitations with a single constraint. Using a triplet purification scheme in combination with the constrained unrestricted Hartree-Fock formalism, scalar-relativistic zero-order regular approximation corrections, and a semiempirical treatment of spin-orbit coupling, COOX is shown to produce highly accurate results for K- and L-edge excitations of second- and third-period atoms with subelectronvolt errors despite being based on LR-TDDFT, for which core excitations pose a well-known challenge. L- and M-edge excitations of heavier atoms up to uranium are also computationally feasible and numerically stable, but may require more advanced treatment of relativistic effects. Furthermore, COOX is shown to perform on par with or better than the popular ΔSCF approach while exhibiting more robust convergence, highlighting it as a promising tool for inexpensive and accurate simulations of X-ray absorption spectra.

Abundant vortex dynamics in spin-1 Bose–Einstein condensates induced by Rashba spin–orbit coupling

The paper studies the dynamics of vortices evolved from the ring dark solitons (RDSs) in spin-1 Bose–Einstein condensates with Rashba spin–orbit coupling (SOC). We find that the SOC induces abundant vortex dynamic phenomena, and the numbers of vortex dipoles and lump-like solitons are all determined by the initial depths’ weighted average of the three components of RDSs. For a shallow RDS, the ring first expands and then contracts into a mini RDS, eventually evolving into late vortex dipoles. For the RDS with a moderate initial depth, during the contraction of the ring, it evolves into early vortex dipoles or lump-like solitons, and they evolve back into the mini RDS, which then evolves into late vortex dipoles during the expansion process. For the deep and black RDSs, the early vortex dipoles continue to transform between vortex dipoles and lump-like solitons without forming mini RDS. The motions of vortices mentioned above have a higher disorder degree than that in the system without SOC, because the SOC breaks the mirror symmetry of the condensate. Finally, we reveal that the SOC strength only influences the number of late vortex dipoles, while it does not affect the number of early vortex dipoles and lump-like solitons. Stronger SOC intensity results in a shallower critical depth, and vortices form only at or beyond this depth.

Resonant spin dynamics of 2D electrons with strong Rashba and Zeeman couplings

Two-dimensional (2D) systems enable enhancing and diversifying the spin–orbit coupling of carriers, a key factor for better charge-spin conversion efficiencies in modern spintronic devices. Increasing 2D spin interactions also modifies dynamical spin-dependent properties of 2D materials, enabling to display resonant phenomena. In this work we focus on dynamical properties of the charge-spin conversion and analyze the resonant spin dynamics of 2D electrons upon strong spin–orbit coupling and Zeeman spin splittings, possibly exceeding the inverse relaxation times of electrons. We derive resonant frequencies and relaxation rates from the Bloch kinetic equations and examine how the trajectories of spin susceptibility poles change with variations in spin splittings and the relaxation time, paying special attention to the interplay between competing Rashba and Zeeman effect.

Magnetic field and photon co-enhanced S-scheme MXene/In2S3/CoFe2O4 heterojunction for high-performance lithium-oxygen batteries

Under the spotlight for their potential to reduce over-potential, photo-assisted Li–O2 batteries still face a key challenge: the rapid recombination of photo-generated electron-hole pairs, which limits their efficiency. In this study, we address this limitation by designing a Li–O2 battery that integrates both photo and magnetic field assistance, using an S-scheme MXene/In2S3/CoFe2O4 heterojunction photocathode. This unique combination enhances visible light absorption and generates a strong built-in electric field, facilitating effective charge separation and boosting photocatalytic activity. During discharge, photo-generated electrons participate in the oxygen reduction reaction, while photo-induced holes contribute to the decomposition of discharge products during charging. Furthermore, the introduction of a magnetic field, confirmed through vibrating sample magnetometer, Mössbauer spectroscopy, X-ray absorption near edge structure, and cyclic voltammetry analyses, enhances electron-hole separation via Lorentz forces and spin–orbit coupling, accelerating the formation and decomposition of Li2O2. With this synergistic approach, the battery achieves a high specific capacity of 26500 mAh g−1, ultra-low oxygen reduction/evolution reaction over-potentials of 0.08 V/0.17 V, and a long cycle life of 2000 cycles with energy efficiency of 98.11 %. This work demonstrates the promising potential of combining photo and magnetic field effects to improve the electrochemical performance of Li–O2 batteries, opening new avenues for high-performance energy storage systems.

Theoretical exploration on the combined effect of isoelectron B-N bonds and B-N resonance skeleton on the thermally activated delayed fluorescence property

The multiple resonance thermally activated delayed fluorescence (MR-TADF) materials has become a hot spot in recent years depending on their potential in achieving an internal quantum efficiency of 100%. The combined effect of para B-N resonance skeleton and isoelectron B-N bonds on the TADF property was investigated in details by employing density functional theory/time-dependent density functional theory (DFT/TDDFT) in this work based on four polycyclic aromatic molecules. The results show that isoelectron B-N bonds are favourable to the enhancement of spin orbital coupling (SOC) constants between the first singlet state (S1) and the first triplet state (T1), while para B-N resonance skeleton is more conducive to reducing the energy gap between S1 and T1 (ΔEST) through realizing short-range charge transfer character and keeping electron and hole localized at different atoms. Accordingly the combination of isoelectron B-N bonds and para B-N resonance skeleton in m[B-N]N1 and m[B-N]N2 could realize faster intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes through larger SOC and lower ΔEST compared with BCz-BN and NBN-2 which only contain para B-N resonance skeleton and isoelectron B-N bonds, respectively. At the same time, the para B-N resonance skeleton help to stabilize the structure of polycyclic aromatic hydrocarbons and localize the vibration in low frequency region during emission from S1 to ground state. Thus larger nonradiative rates induced by the rotation of carbazole and tert-butyl carbazole in low frequency region in m[B-N]N1 and m[B-N]N2 could be easily reduced by replacing them by small functional group such as electron-donating (-CH3) and electron-withdrawing (-CN) groups. Therefore, we can obtain high TADF efficiency through combining para B-N resonance skeleton and isoelectron B-N bonds and suppressing low-frequency vibrations as in our designed molecules m[B-N]CH3 and m[B-N]CN.

Manipulating dwell time and spin polarization via δ-doping for electrons in spin-orbit-coupling modulated magnetic nanostructure

With the help of atomic-layer doping technology, we theoretically explore how to use a δ-potential to manipulate a temporal electron-spin splitter (TESS), which is based on a spin-orbit-coupling (SOC) modulated magnetic nanostructure. Due to the SOC, the dwell time still depends on electron spins even if a δ-doping is embedded inside the TESS. Moreover, both the magnitude and sign of spin polarization ratio can be controlled by tuning the weight or position of the δ-doping. Therefore, a structurally manipulable TESS device can be obtained for semiconductor spintronic device applications.

Investigations of optoelectronic and scintillating properties of novel halide perovskites Cs2KSnX6 (X=Cl, Br, I)

In this paper, using density functional theory (DFT) formalism, optoelectronic properties of new halide perovskites Cs2KSnX6 (X=Cl, Br, I) are explored. The lattice constants of these double perovskites with and were found to be and respectively. Trans-Blaha modified Becke-Johnson (TB-mBJ) exchange-correlation functional was used to calculate the energy bandgap by incorporating spin-orbital coupling effects into it. The double perovskite with was observed to possess a higher band gap value due to the increase in the size of halide anions. Due to the inverse relationship between bandgap values and lattice constants, it has been observed that increasing the lattice constant results in the decrease of the electronic band gap and vice versa. From the density of states calculations, the nature of the electronic states involved in forming the energy bands has been determined. The upper light yield (LY) with the limit of 100% under ideal conditions is found to be 544217 ph/MeV, 950118 ph/MeV, and 1600000 ph/MeV for , and respectively, which suggests their potential applications in scintillating devices. Moreover, the optical properties like complex dielectric functions, absorption coefficients, reflectivity, and refractive index are calculated for these new proposed compounds. A systematic analysis of the optical and scintillating properties suggests the usefulness of among other compounds, as a potential candidate for high-energy radiation detection and other optoelectronic applications.

Enhanced performance of a promising Au/TMDC heterostructure composed of MoTe2 nanosheets decorated with Au5 clusters: A DFT study

This research uses density functional theory approach combined with the spin–orbit coupling to study how the SOx molecules stick to Au5 cluster functionalized MoTe2 nanosheets. In fact, the promising Au/MoTe2 heterostructure system is constructed to model the attachment of gases on its surface. The high efficiency of adsorption process is evident from the strong sticking of the SOx to the Au atoms. Both Au1 and Au5 cluster modified MoTe2 nanosheets revealed semiconducting feature, and in Au5 cluster modified system, the band gap narrowed, while the conductivity is enhanced. Thus, results showed that adding Au cluster to the MoTe2 made it best for adsorbing gases, while MoTe2 without any additives absorbed the gases weakly. The conductivity and recovery time are also analyzed to further describe the results. Based on our theoretical consequences, the Au5 cluster functionalized MoTe2 (Au/MoTe2 heterostructure system) seem good for constructing innovative sensors to detect SOx molecules.

Uncovering bound states in the continuum in InSb nanowire networks

Bound states in the continuum (BICs) are exotic, localized states even though their energy lies in the continuum spectra. Since its discovery in 1929, the quest to unveil these exotic states in charge transport experiments remains an active pursuit in condensed matter physics. Here, we study charge transport in InSb nanowire networks in the ballistic regime and subject to a perpendicular magnetic field as ideal candidates to observe and control the appearance of BICs. We find that BICs reveal themselves as distinctive resonances or antiresonances in the conductance by varying the applied magnetic field and the Fermi energy. We systematically consider different lead connections in hashtag-like nanowire networks, finding the optimal configuration that enhances the features associated with the emergence of BICs. Finally, the investigation focuses on the effect of the Rashba spin–orbit interaction of InSb on the occurrence of BICs in nanowire networks. While the interaction generally plays a detrimental role in the signatures of the BICs in the conductance of the nanowire networks, it opens the possibility to operate these nanostructures as spin filters for spintronics. We believe that this work could pave the way for the unambiguous observation of BICs in charge transport experiments and for the development of advanced spintronic devices.

Designing Quasi-Intrinsic Photosensitizers with Dual Function of Fluorescence Imaging and Photodynamic Therapy.

Photosensitizers (PSs) with effective two-photon absorption in the therapeutic window are the key to two-photon photodynamic therapy. However, the traditional exogenous PSs usually lead to rejection in the body. Besides, the precise visualization of treatments proposes new demands and challenges for the design of PSs. Accordingly, in this work, a series of quasi-intrinsic PSs are obtained based on the artificial base 2-amino-8-(1'-β-d-2'-deoxyribofuranosyl)-imidazo[1,2-α]-1,3,5-triazin-4(8H)-one (P). The calculations show that the structural modification could enhance the two-photon absorption and fluorescence emission, which is beneficial for tumor localization. Furthermore, the reduced singlet-triplet energy gaps and enhanced spin-orbit coupling contribute to the rapid intersystem crossing process, which results in a triplet state with high quantum yields. To ensure the phototherapeutic performance of the newly designed PSs, we also examined the vertical electron affinity and vertical ionization potential for generation of superoxide anions, as well as the T1 energy required to produce singlet oxygen.