Orbital Effects Research Articles

Tuning d-orbitals to control spin-orbit coupling in terminated MXenes.

Theory and experiment have revealed that spin-orbit coupling (SOC) strongly depends on the relativistic effect in topological insulators (TIs), while the influence of orbitals is always ignored. Herein, we provide a direct way of controlling effective SOC with the help of orbital effects, reducing the dependence on elements. Taking 5d W2CO2 and 4d Mo2CO2 MXenes as a specific example, we predict that by decreasing the hybridization strength of W atoms with C or O atoms in 2D W2CO2, the nontrivial bandgaps at the Γ-point are directly enhanced. The weak hybridization of W atoms with ligand elements enhances the electron localization of degenerate d-orbitals of three groups under the triangular prism crystal field, inducing stronger on-site Coulomb repulsion that enhances orbital polarization as well as boosts the SOC effect. Meanwhile, similar results have also been observed in 4d Mo2CO2. This implies that the orbital effects are an efficient and straightforward way to control the nontrivial bandgap in 2D MXene TIs. Our work not only provides an alternative perspective on designing large nontrivial bandgaps but also brings a possibility to control the SOC effect for TI devices.

Large and nonlinear electric field response in a two-dimensional ferroelectric Rashba material

The achievement of electrical spin control is highly desirable. One promising strategy involves electrically modulating the Rashba spin orbital coupling effect in materials. A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors, which is crucial for preserving spin coherence and enhancing integration density. Hence, two-dimensional (2D) Rashba semiconductors with large Rashba constants and significant electric field responses are highly desirable. Herein, by employing first-principles calculations, we design a thermodynamically stable 2D Rashba semiconductor, YSbTe<sub>3</sub>, which possesses an indirect band gap of 1.04 eV, a large Rashba constant of 1.54 eV·Å and a strong electric field response of up to 4.80 e·Å<sup>2</sup>. In particular, the Rashba constant dependence on the electric field shows an unusual nonlinear relationship. At the same time, YSbTe<sub>3</sub> has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier (~ 0.33 eV per formula). By changing the electric polarization direction, the Rashba spin texture of YSbTe<sub>3</sub> can be reversed. These outstanding properties make the ferroelectric Rashba semiconductor YSbTe<sub>3</sub> quite promising for spintronic applications.

Orbital electron delocalization of axial-coordinated modified FeN4 and structurally ordered PtFe intermetallic synergistically for efficient oxygen reduction reaction catalysis.

Regulating the chemical environment of materials to optimize their electronic structure, leading to the optimal adsorption energies of intermediates, is of paramount importance to improving the performance of electrocatalysts, yet remains an immense challenge. Herein, we design a harmonious axial-coordination Pt x Fe/FeN4CCl catalyst that integrates a structurally ordered PtFe intermetallic with an orbital electron-delocalization FeN4CCl support for synergistically efficient oxygen reduction catalysis. The obtained Pt2Fe/FeN4CCl with a favorable atomic arrangement and surface composition exhibits enhanced oxygen reduction reaction (ORR) intrinsic activity and durability, achieving a mass activity (MA) and specific activity (SA) of 1.637 A mgPt -1 and 2.270 mA cm-2, respectively. Detailed X-ray absorption fine spectroscopy (XAFS) further confirms the axial-coupling effect of the FeN4CCl substrate by configuring the Fe-N bond to ∼1.92 Å and the Fe-Cl bond to ∼2.06 Å. Additionally, Fourier transforms of the extended X-ray absorption fine structure (FT-EXAFS) demonstrate relatively prominent peaks at ∼1.5 Å, ascribed to the contribution of the Fe-N/Fe-Cl, further indicating the construction of the FeN4CCl moiety structure. More importantly, the electron localization function (ELF) and density functional theory (DFT) further determine an orbital electron delocalization effect due to the strong axial traction between the Cl atoms and FeN4, resulting in electron redistribution and modification of the coordination surroundings, thus optimizing the adsorption free energy of OHabs intermediates and effectively accelerating the ORR catalytic kinetic process.

Anthracene derivatives with strong spin-orbit coupling and efficient high-lying reverse intersystem crossing beyond the El-Sayed rule.

The attention to materials with hot exciton channel and triplet-triplet fusion (TTF) mediated high-lying reverse intersystem crossing (hRISC) has been raised for their ability to convert non-emissive 'dark' triplets into radiative singlet excitons. This spin conversion process results in high exciton utilization efficiency (EUE) that exceeds the theoretical limits. Notably, it is known that such spin conversion processes from the high-lying excited triplet to the singlet state are facilitated by the orthogonal orbital transition effect governed by the El-Sayed's rule. In this study, an anthracene derivative with indenoquinoline substituent 7,7-dimethyl-9-(10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)-7H-indeno[1,2-f]quinoline (2MIQ-NPA) was synthesized and analyzed to investigate whether the hRISC process occurs in these molecules, even when the El-Sayed's rule is not followed. The hRISC channels of the emitter were fully unraveled through DFT calculations and experiments, which were quantitatively subdivided using transient electroluminescence measurements. The results showed that 2MIQ-NPA, which does not follow the El-Sayed's rule and has a relatively strong spin-orbit coupling matrix element of 0.116 cm-1 between the high-lying triplet state of T4 and the lowest singlet state of S1, effectively converted triplet excitons into singlet excitons with an EUE of 64.3%, contributed by a direct hot exciton channel of 19.2% and a TTF-mediated hot exciton channel of 15.1%. Despite the low outcoupling efficiency, the non-doped device with 2MIQ-NPA achieved an excellent device performance with an external quantum efficiency of 7.0%.

Efficacy and Systemic Effects of a Single Deep Orbital Triamcinolone Injection for Thyroid Eye Disease.

Orbital steroid injections offer a potential therapeutic avenue for managing Thyroid Eye Disease (TED). This study aimed to assess the effectiveness and potential systemic impacts of a single deep orbital triamcinolone injection in TED patients. In a prospective investigation conducted from January 2021 to March 2023, patients diagnosed with TED were enrolled. Inclusion criteria encompassed a Clinical Activity Score (CAS) of ≥3, extraocular muscle inflammation, and upper eyelid retraction. A total of 1 mL of triamcinolone acetonide (40 mg/mL) was administered posterior to the orbital septum at both the medial and lateral aspects of both the upper and lower eyelids. Parameters, including CAS, margin-reflex distances (MRD1 and MRD2), intraocular pressure (IOP), ocular motility (Hess area ratio [HAR%]), exophthalmometry, extraocular muscle size, and blood and urinary indices, were evaluated before and at 2 and 4 weeks after a single injection. Analysis included 28 patients (23 women, 5 men; mean age (SD): 38.7 (11.1) years), representing 56 eyes. Following the injection at 4 weeks, the mean CAS and MRD1 significantly decreased by 2 points and 0.8 mm, respectively. There was a 4.5% increase in HAR%, and extraocular muscle size decreased by 4 to 15.3 mm². Neutrophil count, C-reactive protein, and thyroid antibodies significantly decreased. No severe adverse ophthalmic or systemic effects, including IOP increases or liver damage, were observed. Bilateral single orbital triamcinolone injections provided relief from TED symptoms through both direct effects on orbital soft tissue and systemic effects by decreasing antibody reactions.

The 3d-4f electron transition of the CoS2/CeO2 heterojunction for efficient oxygen evolution.

CoS2/CeO2, exhibiting the 3d-4f orbital coupling effect, is developed and shows exceptional OER activity, with an overpotential of 140 mV at 10 mA cm-2. DFT calculation and Raman spectra show the existence of a d-p-f electron transport ladder that can accelerate electron transfer through the Co-O(S)-Ce bond, optimize the adsorption free energy, and enhance the catalytic activity.

Spin and orbital Edelstein effect in a bilayer system with Rashba interaction

Spin and orbital Edelstein effect in a bilayer system with Rashba interaction

Quantum-mechanical study of a MO2(cyclam)+ complexes series with M = Mn, Tc, Re

This work focuses on the theoretical study of nd2 pentavalent group 7 metal ions (Mn, Tc, Re) electronic structures complexed with cyclam (MO2(cyclam)+) via DFT due to their fascinating photochemical and electrochemical properties. Optical properties were studied via TD-DFT modeling ground (S0) and first excited (S1 and T1) states including spin–orbit effect induced in the absorption and emission spectra. Metal-ligand interactions were studied via EDA-NOCV analysis. DFT suggests increase stability as the metal gets bigger. MLCT and LMCT mechanisms can modulate the optical properties of cyclam ligand and could confer photocatalytic properties under visible light. Deactivation mechanisms shows dark states in all studied complexes. EDA-NOCV results show metal/cyclam interaction with covalent character for all systems, while the metal/oxygens interaction presents large electrostatic character where charge flow happens from cyclam ligand toward nd2-metal orbitals. All theoretical results suggest that MnO2(cyclam)+(a) will display similar properties to reported compounds TcO2(cyclam)+(b) and (ReO2(cyclam)+(c).

Enhancing Ru−Cl interaction via orbital hybridization effect in Ru0.4Sn0.3Ti0.3 electrode for efficient chlorine evolution

Chlorine evolution reaction (CER) is a commercially valuable electrochemical reaction used at an industrial scale. However, oxygen evolution reaction (OER) during the electrolysis process inevitably leads to the decreased efficiency of CER. It is necessary to improve the selectivity of CER by minimizing or even eliminating the occurrence of OER. Herein, a ternary metal oxide (Ru0.4Sn0.3Ti0.3) electrode was fabricated and employed as an active and robust anode for CER. The Ru0.4Sn0.3Ti0.3 electrode exhibits an excellent CER performance in 6.0 M NaCl solution, with a low potential of 1.17 V (vs. saturated calomel electrode, SCE) at 200 mA cm−2 current density, a high Cl2 selectivity of over 90 %, and robust durability after consecutive operation for 160 h under 100 mA cm−2. The maximum O2-Cl2 potential difference between OER and CER further demonstrates the high Cl2 selectivity of Ru0.4Sn0.3Ti0.3 electrode. Theoretical studies show that the strong Ru 3d−Ti 3d orbitals hybridization effect makes the d-band center (εd) of Ru 3d and Ti 3d orbitals positively and negatively shifted, respectively, endowing Ru site with enhanced Cl adsorption ability (i.e. enhanced Ru−Cl interaction) and Ru0.4Sn0.3Ti0.3 electrode with superior CER activity. This work offers valuable insights into the development of advanced electrodes for CER in practical application.

Strong p-d Orbital Hybridization on Bismuth Nanosheets for High Performing CO2 Electroreduction.

Single-atom alloys (SAAs) show great potential for a variety of electrocatalytic reactions. However, the atomic orbital hybridization effect of SAAs on the electrochemical reactions is unclear yet. Herein, the in situ confinement of vanadium/molybdenum/tungstenatoms on bismuth nanosheet is shown to create SAAs with rich grain boundaries, respectively. With the detailed analysis of microstructure and composition, the strong p-d orbital hybridization between bismuth and vanadium enables the exceptional electrocatalytic performance for carbon dioxide (CO2 ) reduction with the Faradaic efficiency nearly 100% for C1 products in a wide potential range from -0.6 to -1.4V, and a long-term electrolysis stability for 90h. In-depth in situ investigations with theoretical computations reveal that the electron delocalization toward vanadium atoms via the p-d orbital hybridization evokes the bismuth active centers for efficient CO2 activation via the σ-donation of O-to-Bi, thus reduces protonation energy barriers for formate production. With such fundamental understanding, SAA electrocatalyst is employed to fabricated the solar-driven electrolytic cell of CO2 reduction and 5-hydroxymethylfurfural oxidation, achieving an outstanding 2,5-furandicarboxylic acid yield of 90.5%. This study demonstrates a feasible strategy to rationally design advanced SAA electrocatalysts via the basic principles of p-d orbital hybridization.

Rotating Alfvén waves in rotating plasmas

Angular momentum coupling between a rotating magnetized plasma and torsional Alfvén waves carrying orbital angular momentum (OAM) is examined. It is demonstrated not only that rotation is the source of Fresnel–Faraday rotation – or orbital Faraday rotation effects – for OAM-carrying Alfvén waves, but also that angular momentum from an OAM-carrying Alfvén wave can be transferred to a rotating plasma through the inverse process. For the direct process, the transverse structure angular rotation frequency is derived by considering the dispersion relation for modes with opposite OAM content. For the inverse process, the torque exerted on the plasma is derived as a function of wave and plasma parameters.

The post-Newtonian motion around an oblate spheroid: the mixed orbital effects due to the Newtonian oblateness and the post-Newtonian mass monopole accelerations

The post-Newtonian motion around an oblate spheroid: the mixed orbital effects due to the Newtonian oblateness and the post-Newtonian mass monopole accelerations

Current-Induced Magnetization Switching in Light-Metal-Oxide/Ferromagnetic-Metal Bilayers via Orbital Rashba Effect.

The orbital angular momentum (OAM) generation as well as its associated orbital torque is currently a matter of great interest in spin-orbitronics and is receiving increasing attention. In particular, recent theoretical work predicts that the oxidized light metal Cu can serve as an efficient OAM generator through its surface orbital Rashba effect. Here, for the first time, the crucial current-induced magnetic-field-free in-plane magnetization reversal is experimentally demonstrated in CoFeB/CuOx bilayers without any heavy elements. We show that the critical current density can be comparable to that of strong spin-orbit coupling systems with heavy metals (Pt and Ta) and that the magnetization reversal mechanism is governed by coherent rotation in the grains through the second-harmonic and magneto-optical Kerr effect measurements. Our results indicate that light metal oxides can play an equally important role as heavy metals in magnetization reversal, broadening the choice of materials for engineering spintronic devices.

Can simple 'molecular' corrections outperform projector augmented-wave density functional theory in the prediction of 35 Cl electric field gradient tensor parameters for chlorine-containing crystalline systems?

Many-body expansion (MBE) fragment approaches have been applied to accurately compute nuclear magnetic resonance (NMR) parameters in crystalline systems. Recent examples demonstrate that electric field gradient (EFG) tensor parameters can be accurately calculated for 14 N and 17 O. A key additional development is the simple molecular correction (SMC) approach, which uses two one-body fragment (i.e., isolated molecule) calculations to adjust NMR parameter values established using 'benchmark' projector augmented-wave (PAW) density functional theory (DFT) values. Here, we apply a SMC using the hybrid PBE0 exchange-correlation (XC) functional to see if this can improve the accuracy of calculated 35 Cl EFG tensor parameters. We selected eight organic and two inorganic crystal structures and considered 15 chlorine sites. We find that this SMC improves the accuracy of computed values for both the 35 Cl quadrupolar coupling constant (CQ ) and the asymmetry parameter ( ) by approximately 30% compared with benchmark PAW DFT values. We also assessed a SMC that offers local improvements not only in terms of the quality of the XC functional but simultaneously in the quality of the description of relativistic effects via the inclusion of spin-orbit effects. As the inorganic systems considered contain heavy atoms bonded to the chlorine atoms, we find further improvements in the accuracy of calculated 35 Cl EFG tensor parameters when both a hybrid functional and spin-orbit effects are included in the SMC. On the contrary, for chlorine-containing organics, the inclusion of spin-orbit relativistic effects using a SMC does not improve the accuracy of computed 35 Cl EFG tensor parameters.

Effects of electron–phonon coupling and Rashba spin–orbit interaction on thermodynamic and magnetic properties of quantum dots

The thermodynamic and magnetic properties of quantum-dot structures subjected to an applied magnetic field were studied, including the longitudinal optical–phonon interaction and the Rashba spin–orbit effect. The Schrödinger equation was solved to determine the energy levels. The partition function was evaluated by summing the accessible energy levels and was then utilized to calculate the thermomagnetic functions. In this paper, we present magnetic properties by considering three interacting polarons. Our results indicated that at B=0T, the susceptibility exhibits diamagnetic behavior for all values of the Rashba spin–orbit parameter. However, the magnetic susceptibility increases with an applied magnetic field, and the system exhibits paramagnetic behavior under moderate magnetic fields. However, in situations with and without the polaron effect, the susceptibility is saturated at 0(meV/T2) under large magnetic fields. In this study, we showed that the Rashba spin–orbit interaction (SOI) strengthens the cutoff magnetic field Bc (the B value at which the magnetic nature of the dot changes from diamagnetic to paramagnetic). Rashba SOIs reduce the mean energy of the system, including polaronic interactions. Under the polaron effect, the heat capacity curve shifts to lower temperatures. A quantitative description of the magnetocaloric effect (ΔS) as a function of the Wigner and Rashba spin–orbit parameters is presented.

Engineering High-Spin State Cobalt Cations in Sulfide Spinel for Enhancing Water Oxidation.

The spin states of active sites have a significant impact on the adsorption/desorption ability of the reaction intermediates during the oxygen evolution reaction (OER). Sulfide spinel is not generally considered a highly efficient OER catalyst owing to the low spin state of Co3+ and the lack of unpaired electrons available for adsorption of reaction intermediates. Herein, it is proposed a novel Nd-evoked valence electronic adjustment strategy to engineer the spin state of Co ions. The unique f-p-d orbital electronic coupling effect stimulates the rearrangement of Co d orbital electrons and increases the eg electron filling to achieve high-spin state Co ions, which promotes charge transport by propagating a spin channel and generates a high number of active sites for intermediate adsorption. The optimized CuCo1.75 Nd0.25 S4 catalyst exhibits outstanding electrocatalytic properties with a low overpotential of 320mV at 500mAcm-2 and a 48h stability at 300mAcm-2 . In situ synchrotron radiation infrared spectra confirm the quick accumulation of key *OOH and *O intermediates. This work deepens the comprehensive understanding of the relationship between OER activity and spin configurations of Co ions and offers a new design strategy for spinel compound catalysts.

Enhancement of nonlinear optical properties of nanocarbon cluster C60 by aluminum doping

AbstractThe search for good nonlinear optical (NLO) materials is of utmost importance in laser technology and optical information science, making it a popular research topic in materials science. It is reported that the introduction of alkali metal Li can enhance the NLO properties of nanocarbon materials. Here, metal Al, which exhibits similar electron transfer characteristics to Li, was used for the first time to enhance the NLO properties of nanocarbon cluster C60, which possesses a large delocalized π structure and the highest yield in the fullerene family. Density functional theory calculations in combination with Boltzmann distribution showed that the most thermodynamically stable Al@Ih(1812)‐C60 exhibited good second‐order NLO properties, which originated from the noncentrosymmetry geometry and one extra delocalized electron on Ih(1812)‐C60 from the 3p shell of inner Al. Density of state analysis indicated that the molecular orbitals of Al@Ih(1812)‐C60 were primarily formed by Ih(1812)‐C60 with minimal Al participation, and the presence of Al always resulted in an antibonding orbital effect. Bond critical point and electron localization function analyses indicated almost no covalent interaction between Al and Ih(1812)‐C60. Exohedral functionalization was employed to further stabilize Al@Ih(1812)‐C60 with radical character, and the infrared spectrum was also analyzed in detail. This study has promising implications for expanding the potential applications of fullerenes in optical devices.

Electron–phonon interaction and electronic correlations in transport through electrostatically and tunnel coupled quantum dots

We investigate two equivalent capacitively and tunnel coupled quantum dots, each coupled to its own pair of leads. Local Holstein type electron–phonon coupling at the dots is assumed. To study many-body effects we use the finite-U mean-field slave boson approach. For vanishing interdot interaction, weak e–ph coupling and finite tunneling, molecular orbital spin Kondo effects occur for single electron or single hole occupations. Phonons influence both correlations and tunneling and additionally they shift the energies of the dots. Depending on the dot energies and the strength of electron–phonon coupling, the system is occupied by a different number of electrons that effectively interact with each other repulsively or attractively leading to a number of different ground states of DQD. Among them are Kondo-like states with spin, orbital or charge correlations resulting from polaron cotunneling processes and states with magnetic intersite correlations.

Synergistic activation of P and orbital coupling effect for ultra-sensitive and selective electrochemical detection of Cd(II) over Fe-doped CoP

Despite significant advancements in the detection of cadmium (Cd(II)) based on nanomaterial adsorbability, limited research has been conducted on ultra-sensitive and selective detection mechanisms, resulting in a lack of guidance for designing efficient interface materials to detect Cd(II). Herein, reductive Fe doping on CoP facilitates an efficient Fe-Co-P electron transfer path, which renders P the electron-rich site and subsequently splits a new orbital peak that matches with that of Cd(II) for excellent electrochemical performance. The sensitivity of Cd(II) was remarkably up to 109.75 μA μM−1 on the Fe-CoP modified electrode with excellent stability and repeatability, surpassing previously reported findings. Meanwhile, the electrode exhibits exceptional selectivity towards Cd(II) ions compared to some bivalent heavy metal ions (HMIs). Moreover, X-ray absorption fine structure (XAFS) analysis reveals the interaction between P and Cd(II), which is further verified via density functional theory (DFT) calculation with the new hybrid peaks resulting from the splitting peak of P atoms coupled with the orbital energy level of Cd(II). Generally, doping engineering for specific active sites and regulation of orbital electrons not only provides valuable insights for the subsequent regulation of electronic configuration but also lays the foundation for customizing highly sensitive and selectivity sensors.

Excitonic effects on the optical spectra of TiB2 nanosheets

Two-dimensional (2D) transition metal borides, have recently attracted tremendous interest and become an emerging class of 2D materials due to their intriguing properties. We report systematic investigation of stability, electronic properties and optical activity of 2D-TiB2 nanosheets using first-principles calculations. By combining elastic and phonon-dispersion calculations, we substantiated the mechanical and dynamic stability of 2D-TiB2 nanosheets. Our results of elastic calculations reveal that addition of an extra layer destroys the auxetic behaviour of monolayer (ML) 2D-TiB2 with significant reduction in the brittleness. Further, based on the spin-polarised electronic structure calculations, we find that a low-dimensional metallic state of ML can be achieved by tuning the distance between the titanium and boron layers. The calculations clearly reveal that metallic nature does not destroys the auxetic behaviour of ML. Subsequently, we investigated the optical response of 2D-TiB2 nanosheets (ML and bilayer (BL)) at the level of density functional theory and many-body perturbation theory. The results obtained by solving Bethe–Salpeter equation (GW+BSE formalism) shows that excitonic effects causes a slight blue-shift in the absorption spectra of the nanosheets with ML being optically active with sharp peaks in infrared (IR) and ultraviolet (UV) regions while BL shows the reduced optical activity across wide range of photon energies spanning the near-IR to UV region. In addition, electronic polarisability of the nanosheet decreases with addition of another layer in ML 2D-TiB2. Further investigation of transition probabilities clearly indicates that the response of ML at Dirac point is tunable by spin–orbital coupling effects which makes these nanosheets promising for spintronic applications. The BL exhibits distinct electronic, and optical properties compared to ML. Our study unravels the structural, elastic, electronic, and optical properties of 2D-TiB2 nanosheets and suggests them as promising candidate for variety of optoelectronic and spintronic applications.