Spin-orbit Coupling Effects Research Articles

Theoretical MRCI + Q study on electronic structure and spectroscopic properties of the HX+(X = F, Cl, Br, I) cations

In this work, we have systematacially investigated the electronic structure and spectroscopic properties of the HX+ (X = F, Cl, Br, I) cations by using the highly correlated MRCI + Q approach. This is the first comprehensive ab initio study on the electronic states of the HX+ cations. The spin–orbit coupling (SOC) effect is introduced with the state interaction approach. There are total 10 Λ-S and 18 Ω states obtained in the calculation. The results show that the potential energy curves’ (PECs) shapes and structure of the electronic states of different HX+ cations exhibit the significant distinction due to the X-dependent energy-level order of the unique dissociation channel H+(1Sg) + X(2Pu). From PECs, the spectroscopic constants of the bound electronic states are determined, which are in good agreement with available observed values. Regarding HBr+ and HI+, the good agreement has been achieved only when the SOC effect is considered. The predissociation for the first excited A2Σ+ state of HCl+, HBr+, and HI+ is analyzed based on computed spin–orbit matrix elements. Around the equilibrium position, the energy splittings of X2Π are calculated to be 288, 661, 2691, and 5137 cm−1 for HF+, HCl+, HBr+, and HI+, respectively. It has been demonstrated that SOC is substantial for HX+, leading to significant changes in PECs’ shapes as well as in electronic structure. Finally, the transition properties are predicted, including transition dipole moments, Franck–Condon factors, and radiative lifetimes. Both the Ω transitions A2Σ+ 1/2-X2Π3/2 and A2Σ+ 1/2-X2Π1/2 of the HX+ cations are determined to possess the radiative lifetimes at the microsecond (µs) level.

The unique geometries and magnetic anisotropy energy of FenPt (n = 3–13) clusters: A first-principles investigation

Enthusiasm for exploring magnetic anisotropy energy (MAE) and spin–orbit coupling (SOC) effects in magnetic studies of transition metal alloy clusters remains high. In this paper, the first-principle method was used to investigate the global minimum energy structure of FenPt (n = 3–13) clusters and their interesting magnetic properties. Comparative structural analyses show that FenPt (n = 3–13) clusters have unique structures, and their relative stability analyses indicate that the increase in the number of atoms influences the geometrical arrangement of the clusters. The exploration of magnetic properties has focused on two areas. First, FenPt (n = 3–13) is found to have a large magnetic moment, while the magnetic moment increment surprisingly varies in the same way in different cases with and without the inclusion of SOC effects. Second, the calculations show that FenPt (n = 3, 4, 9, 13) has MAE, ranging from 1.420-2.687 meV/atom. The SOC matrix results show the interaction of Pt dx2-y2 and Pt dxy, and the interaction of Pt dz2 and Pt dyz, exhibit an indispensable force in determining the MAE.

Triplet Excited State Mechanistic Study of meso‐Substituted Methylthio Bodipy Derivative: Time‐Resolved Optical and Electron Paramagnetic Resonance Spectral Studies

AbstractUnderstanding the intersystem crossing (ISC) mechanism of organic compounds is essential for designing new triplet photosensitizers. Herein, we investigated the ISC mechanism of a heavy atom‐free Bodipy derivative with thiomethyl substitution (S−BDP). A long‐lived triplet state was observed with nanosecond transient absorption spectroscopy with lifetime of 7.5 ms in a polymer film and 178 μs intrinsic lifetime in fluid solution, much longer as compared with what was previously reported (apparent triplet lifetime=15.5 μs). Femtosecond transient absorption studies retrieved an ISC time constant of ∼3 ns. Time‐resolved electron paramagnetic resonance (TREPR) indicated a special triplet electron spin polarization phase (ESP) pattern (a, e, a, e, a, e) for S−BDP, different from the ESP (e, e, e, a, a, a) typical for the spin‐orbital coupling (SOC) mechanism. This indicates that the electron spin selectivity of the ISC of S−BDP is different from that of the normal SOC effect in iodo‐Bodipy. Simulations of the TREPR spectra give a zero‐field‐splitting D parameter of −2257 MHz, much smaller as compared to the reference 2,6‐diiodo‐Bodipy (D=−4380 MHz). The computed SOC matrix elements (0.28–1.59 cm−1) and energy gaps for the S1/Tn states suggest that the energy matching between the S1 and T2/T3 states (supported by the largest kISC ∼109 s−1) enhances the ISC for this compound.

Insights into the Mechanism of Chiral-Induced Spin Selectivity: The Effect of Magnetic Field Direction and Temperature.

Chiral oligopeptide monolayers are adsorbed on a ferromagnetic surface and their magnetoresistance is measured as a function of the angle between the magnetization of the ferromagnet and the surface normal. These measurements are conducted as a function of temperature for both enantiomers. The angle dependence is found to follow a changing trend with a period of 360°. Quantum simulations reveal that the angular distribution can be obtained only if the monolayer has significant effective spin orbit coupling (SOC), that includes contribution from the vibrations. The model shows that SOC only in the leads cannot reproduce the observed angular dependence. The simulation can reproduce the experiments if it included electron-phonon interactions and dissipation.

Investigation of Isolated IrF5 -, IrF6 - Anions and M[IrF6] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF5 -, IrF6 - anions and M[IrF6] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF6 and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF6 with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6 - and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6 - anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding "closed-shell" M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M=Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7 - or M[IrF7] (M=Na, K, Rb, Cs) ion pairs in our experiments.

The electronic structures and optical properties induced by spin-orbit-coupling in LiPbPO4 compound

Phosphate materials are excellent candidates for nonlinear optical materials, thus necessitating a comprehensive and in-depth study of them. Here, inspired by the interesting phenomenon induced by the spin-orbit coupling (SOC) effect, we extend it to LiPbPO4 compounds using a first-principles approach to probe the influence of SOC on the electronic structure and optical properties of post-transition metal compounds. The results show that only the bottom of the conduction band shows an energy level splitting with the inclusion of SOC, which is analyzed to come from the SOC in the Pb 6p state since the SOC in the O 2p state is very weak. The splitting of the conduction band triggers the decrease of the band gap and the change of the optical properties. The performance analysis shows that both the refractive index and the second harmonic generation (SHG) coefficient are enhanced with the inclusion of SOC, however, the change in the birefringence is insignificant, and it is further found that the enhanced SHG coefficient values are closer to the experimental values. In conclusion, our study reveals the impact of SOC effect on the electronic structure and optical properties of LiPbPO4 compounds, contributing to a deeper understanding of the nonlinear optical in post-transition metal compounds.

Intrinsic valley-polarized quantum anomalous Hall effect in a two-dimensional germanene/MnI2 van der Waals heterostructure

Abstract Valley-polarized quantum anomalous Hall effect (VQAHE), combined nontrivial band topology with valleytronics, is of importance for both fundamental sciences and emerging applications. However, the experimental realization of this property is challenging. Here, by using first-principles calculations and modal analysis, we predict a mechanism of producing VQAHE in two-dimensional ferromagnetic van der Waals germanene/MnI2 heterostructure. This heterostructure exhibits both valley anomalous Hall effect and VQAHE due to the joint effects of magnetic exchange effect and spin–orbital coupling with the aid of anomalous Hall conductance and chiral edge state. Moreover interestingly, through the electrical modulation of ferroelectric polarization state in In2Se3, the germanene/MnI2/In2Se3 heterostructure can undergo reversible switching from a semiconductor to a metallic behavior. This work offers a guiding advancement for searching for VQAHE in ferromagnetic van der Waals heterostructures and exploiting energy-efficient devices based on the VQAHE.

Anisotropic RKKY interaction in doped monolayer germanene: spin–orbit coupling effects

Anisotropic RKKY interaction in doped monolayer germanene: spin–orbit coupling effects

Polarization-Addressable Optical Movement of Plasmonic Nanoparticles and Hotspot Spin Vortices.

Spin-orbit coupling in nanoscale optical fields leads to the emergence of a nontrivial spin angular momentum component, transverse to the orbital momentum. In this study, we initially investigate how this spin-orbit coupling effect influences the dynamics in gold monomers. We observe that localized surface plasmon resonance induces self-generated transverse spin, affecting the trajectory of the nanoparticles as a function of the incident polarization. Furthermore, we investigate the spin-orbit coupling in gold dimers. The resonant spin momentum distribution is characterized by the unique formation of vortex and anti-vortex spin angular momentum pairs on opposite surfaces of the nanoparticles, also affecting the particle motion. These findings hold promise for various fields, particularly for the precision control in the development of plasmonic thrusters and the development of metasurfaces and other helicity-controlled system aspects. They offer a method for the development of novel systems and applications in the realm of spin optics.

Numerical simulation of Rashba spin–orbit coupling effect on quantum Hall resistivity within tight-binding approximation

A numerical simulation of the effect of Rashba spin–orbit coupling (RSO) on quantum transport properties of electrons confined to a two-dimensional electron gas (2DEG) in the integer quantum Hall regime is presented. The mechanism of quantization and the dependence of the Hall resistivity (HR) on the system built-in and external parameters are studied using the non-equilibrium Green’s function (NEGF) technique. Relevant Green’s functions are computed numerically using spectral decomposition method in combination with recursive techniques. The tight-binding-like representation of the system Hamiltonian including magnetic field is obtained within the finite difference method, using Dirichlet boundary conditions. Corresponding formula linking the Hall resistivity with the transmission function of the system has been derived analytically within the NEGF formalism in a general form, in the sense that the formula can also be used beyond the linear response limit and for nonzero temperatures. In particular, it was shown explicitly that in the presence of the RSO coupling the even- and odd plateaus emerging in the magnetic-field dependence of the quantum Hall resistivity are related to different physical mechanisms.

Effect of spin-orbit coupling and impurities on the optical properties of double quantum rings under magnetic fields

In this paper, the energy spectrum of concentric double quantum rings (CDQRs) with double well confinement under the influence of spin-orbit interactions (SOIs), magnetic fields, and hydrogen donor impurities is studied by using diagonalization. The light absorption coefficient is then calculated in the form of a compactness density-matrix. Key findings from this study include the ability to manipulate fine energy level splitting and optical absorption coefficients by tuning the magnetic field, impurity position, spin-orbit coupling, and inner rings size. Furthermore, this study reveals the bleaching effect of the optical absorption coefficient under certain conditions and demonstrates the anisotropic nature of the system through changes in the optical absorption coefficients (OACs) for different incident light polarization angles.

Spontaneous polarization dynamics in V-doped monolayer MoS2

Valleytronics has drawn attention both for its fundamental aspects and potential applications in device technology. Lifting the valley degeneracy is an attractive route to achieve stable valley polarization and spontaneous valley polarization. Our first-principles calculations on V-doped monolayer MoS2 reveal a substantial permanent valley splitting of 174 meV, driven by the combined effects of spin-orbit coupling (SOC) and magnetic coupling with the doped atom. Non-adiabatic molecular dynamics simulations show that the spontaneous valley polarization dynamics depends on the SOC, electron-phonon (e-ph) coupling and the scattering with the impurity, and it varies notably with different initial spin orientations of excited holes. For spin-up holes, the process involves e-ph scattering and spin-flip induced by spinor-phonon scattering over several picoseconds. On the other hand, spin-down hole excitation leads to spontaneous polarization through e-ph and impurity scattering on a timescale shorter by an order of magnitude. This study provides insights into the distinct valley polarization dynamics of carriers with different spins, contributing to the design of ultrafast valleytronic and spintronic devices.

Landau Theory of Altermagnetism.

We formulate a Landau theory for altermagnets, a class of collinear compensated magnets with spin-split bands. Starting from the nonrelativistic limit, this Landau theory goes beyond a conventional analysis by including spin-space symmetries, providing a simple framework for understanding the key features of this family of materials. We find a set of multipolar secondary order parameters connecting existing ideas about the spin symmetries of these systems, their order parameters, and the effect of nonzero spin-orbit coupling. We account for several features of canonical altermagnets such as RuO_{2}, MnTe, and CuF_{2} that go beyond symmetry alone, relating the order parameter to key observables such as magnetization, anomalous Hall conductivity, and magnetoelastic and magneto-optical probes. Finally, we comment on generalizations of our framework to a wider family of exotic magnetic systems derived from the zero spin-orbit coupled limit.

Spin–orbit coupling tunable electronic properties of [formula omitted]-MoS[formula omitted] and ternary Janus [formula omitted]-MoSSe monolayers: Theoretical prediction

MoS2 can exist in many different polytypes, such as trigonal prismatic, distorted octahedral, or octahedral. The 2H-phase of MoS2 has been extensively studied in recent times, but there are very few studies focusing on the remaining phases, especially the distorted octahedral T′)-phase. Here, we design the MoS2 monolayer and Janus MoSSe structure in the 1T′ phase and study their electronic properties within the framework of first-principles calculations. Both 1T′-MoS2 and 1T′-MoSSe monolayers are confirmed to have structural stability and anisotropic mechanical characteristics. Interestingly, while the 1T′-MoS2 monolayer exhibits metallic characteristics, Janus MoSSe in the 1T′ phase is a semiconductor with a small band gap of 0.04 eV. More interestingly, a tiny bandgap of 0.05 eV has opened up in the 1T′-MoS2 monolayer due to the spin–orbit coupling effect. We also study the mobility of carriers in the semiconductor Janus 1T′-MoSSe monolayer. 1T′-MoSSe monolayer exhibits a high anisotropic carrier mobility due to its high anisotropic crystal structure. Surprisingly, 1T′-MoSSe monolayer possesses extremely high electron mobility, up to 4.58×103 cm2 V−1 s−1. Our findings give a deeper insight into the 1T′-phase of transition metal dichalcogenide and its Janus structure.

Structural Isomeric Effect on Spin Transport in Molecular Semiconductors.

Molecular semiconductor (MSC) is a promising candidate for spintronic applications benefiting from its long spin lifetime caused by light elemental-composition essence and thus weak spin-orbit coupling (SOC). According to current knowledge, the SOC effect, normally dominated by the elemental composition, is the main spin-relaxation causation in MSCs, and thus the molecular structure-induced SOC change is one of the most concerned issues. In theoretical study, molecular isomerism, a most prototype phenomenon, has long been considered to possess little difference on spin transport previously, since elemental compositions of isomers are totally the same. However, here in this study, quite different spin-transport performances are demonstrated in ITIC and its structural isomers BDTIC experimentally, for the first time, though the charge transport and molecular stacking of the two films are very similar. By further experiments of electron-paramagnetic resonance and density-functional-theory calculations, it is revealed that noncovalent-conformational locks (NCLs) formed in BDTIC can lead to enhancement of SOC and thus decrease the spin lifetime. Hence, this study suggests the influences from the structural-isomeric effect must be considered for developing highly efficient spin-transport MSCs, which also provides a reliable theoretical basis for solving the great challenge of quantificational measurement of NCLs in films in the future.

Ab Initio Study on Electronic Excited States of Monochlorosilylene.

We perform a high-level ab initio study on 20 electronic states of monochlorosilylene (HSiCl) using an internally contracted multireference configuration interaction method including Davidson correction (icMRCI+Q). The spin-orbit coupling (SOC) effect is investigated, leading to splitting of the 20 spin-orbit-free states into 50 spin-orbit-coupled states. Vertical transition energies, oscillator strengths, and potential energy curves are presented with and without considering the SOC effect. Analysis indicates that the SOC effect plays an important role, especially for the high-lying excited states of HSiCl. The state interaction and the dynamics of the electronic states of HSiCl in the ultraviolet region are discussed based on our calculation results. Our study paves the way to understanding the behavior of electronic excited states of monochlorosilylene.

High-Resolution Rovibronic Cross Sections of the MgH+ Molecular Cation.

The high-resolution rovibronic line lists of the MgH+ molecular cation are presented in our work. The potential energy curves are calculated by the method of multireference configuration interaction and Davidson correction (MRCI+Q) with the spin-orbit coupling (SOC) effect. Spectroscopy constants are fitted and the results are in good agreement with experiments, ensuring the accuracy of the electronic structure. On account of potential energy curves and transition dipole moments, the Franck-Condon factors and Einstein coefficients of transition are obtained. These calculations are used to obtain an accurate partition functions and line lists for molecules. Using the partition functions and line lists, the absorption cross-sections under different temperatures and pressures were simulated. Our work could provide some theoretical insights into solar and cold planet spectrum.

Slow magnetic relaxation in a europium(II) complex.

Single-ion anisotropy is vital for the observation of Single-Molecule Magnet (SMM) properties (i.e., a slow dynamics of the magnetization) in lanthanide-based systems. In the case of europium, the occurrence of this phenomenon has been inhibited by the spin and orbital quantum numbers that give way to J = 0 in the trivalent state and the half-filled population of the 4f orbitals in the divalent state. Herein, by optimizing the local crystal field of a quasi-linear bis(silylamido) EuII complex, the [EuII(N{SiMePh2}2)2] SMM is described, providing an example of a europium complex exhibiting slow relaxation of its magnetization. This behavior is dominated by a thermally activated (Orbach-like) mechanism, with an effective energy barrier of approximately 8 K, determined by bulk magnetometry and electron paramagnetic resonance. Ab initio calculations confirm second-order spin-orbit coupling effects lead to non-negligible axial magnetic anisotropy, splitting the ground state multiplet into four Kramers doublets, thereby allowing for the observation of an Orbach-like relaxation at low temperatures.

Spin–orbit coupling effects on localization and correlated tunneling for two interacting bosons in a double-well potential

We theoretically study the tunneling dynamics of two interacting spin–orbit-coupled (SOC) atoms trapped in a periodically perturbed double-well potential. We find that the phenomenon of coherent destruction of tunneling (CDT) can exist only for certain values of SOC, and two different mechanisms for the appearance of CDT are identified in this system. One is the conventional CDT resulting from quasi-energy degeneracy, while the other CDT originates from the dark Floquet state with zero quasi-energy for all values of the driving parameters. We discover that under double modulation combining the double-well potential shaking and a time-periodic Zeeman field, it is possible to realize spin-flipping single-atom Rabi tunneling and the CDT induced by the dark Floquet state at any value of SOC strength, which is not accessible with a single-drive field. Furthermore, we show that the detuning of Zeeman field with respect to the multiphoton energy is particularly significant in the case of the correlated two-particle tunneling mediated by SOC. We expect that these results will stimulate further exploration of the many-body dynamics in the interacting systems and expand the possibilities for manipulating the spin dynamics.

Tuning the physical properties of inorganic novel perovskite materials Ca3PX3 (X=I, Br and Cl): Density function theory

In photovoltaic technology, inorganic perovskite solar cells formed from halide have developed into a noteworthy prospect, primarily attributable to their exceptional efficiency, cost-effectiveness, and straightforward manufacturing techniques. Lead-free A3BX3 inorganic perovskites have generated significant attention within the environmentally friendly solar industry thanks to their extraordinary characteristics encompassing thermoelectricity, optoelectronics, and elasticity. This research focuses on the attributes of the structural, electrical, and optical inorganic halide perovskites Ca3PX3 (X = I, Br, and Cl) using the first-principles density-functional theory (FP-DFT). According to the electronic band structures, Ca3PI3, Ca3PBr3, and Ca3PCl3 show semiconductor characteristics with a straight bandgap of 1.4909 eV, 1.9502 eV, and 2.2058 eV, respectively, at the Γ(gamma)-point. Whenever one takes consideration into account the spin-orbital coupling (SOC) effect, the bandgap of the Ca3PI3, Ca3PBr3, and Ca3PCl3 perovskites is minimized to 1.2382 eV, 1.6456 eV, and 1.9056 eV. All these structures' bandgaps are compressed under compressive strain while they expand with tensile strain. The optical properties indicate that these materials have outstanding visible light consumption capabilities due to their distinct band features, comprising functions of dielectric, consumption coefficient, and function of electron collapse. Observations indicate that the dielectric constant peaks of Ca3PX3 (where X represents I, Br, or Cl) exhibit a redshift, moving towards lower photon energy levels as compressive strain increases. Conversely, they show a blueshift behavior, shifting to a greater amount of photon energy levels by applying tensile strain. Therefore, these characteristics render Ca3PX3 perovskites highly suitable for optimizing light guidance for solar power and energy retention tools.