Understanding the mechanisms underlying the emergence of giant spin splitting (GSS) is fundamental in the pursuit of more robust strategies for designing materials with desired spin splitting. This drive for material innovation continues to captivate a burgeoning community of early-career researchers with backgrounds in chemistry and material science. However, new to the field, they are often equipped only with the insight provided by the original Bychkov-Rashba model. Furthermore, daunted by the tight-binding perspective on the non-vanishing orbital angular momentum (OAM), they struggle to accurately account for the atomic spin-orbit interaction (SOI) in the formation of GSS. To address these challenges and equip young chemists with better-suited tools, this review aims to provide a more intuitive perspective on atomic interactions (orbital hybridization), structure symmetry, and atomic SOI in the formation of GSS. In pursuit of this goal, the review explores the Bychkov-Rashba model, its advantages, and limitations. Subsequently, it introduces the orbital framework, wherein GSS is modulated by atomic SOI and the interplay of OAM with the surface electrostatic field. Given the explicit dependence of both these factors on OAM, the review examines why OAM is typically quenched in crystal structures and how chemical bonds involving different orbital types can lead to its non-zero values in the presence of inversion symmetry breaking. Finally, with this chemistry-focused perspective, the review examines the rise of GSS in selected examples.
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http://dx.doi.org/10.1039/d3cp04242a | DOI Listing |
Phys Rev Lett
December 2024
Clermont INP, Institut Pascal, PHOTON-N2, Université Clermont Auvergne, CNRS, F-63000 Clermont-Ferrand, France.
The combination of an in-plane honeycomb potential and of a photonic spin-orbit coupling (SOC) emulates a photonic or polaritonic analog of bilayer graphene. We show that modulating the SOC magnitude allows us to change the overall lattice periodicity, emulating any type of moiré-arranged bilayer graphene with unique all-optical access to the moiré band topology. We show that breaking the time-reversal symmetry by an effective exciton-polariton Zeeman splitting opens a large topological gap in the array of moiré flat bands.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institut für Anorganische Chemie and International Center for Advanced Studies of Energy Conversion, Georg-August-Universität Göttingen, Tammannstr 4, 37077 Göttingen, Germany.
Nitrenes (R-N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R-Pn; Pn = P-Bi) are much less systematically explored.
View Article and Find Full Text PDFAdv Mater
January 2025
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China.
Nanomagnetism may enable electrical conductivity and Seebeck coefficient to be decoupled and can potentially lead to remarkable enhancements in thermoelectric (TE) performance, however, their physical mechanisms have not been explored. Herein, it is shown that the nanomagnetism from Fe and FeO nanoparticles embedded in BiSbTe/epoxy flexible films can lead to the carriers splitting into spin-up and spin-down conductive branches with different resistances and mobilities due to the exchange interaction between the spin of carriers and the nanomagnetism. The double-resistance conduction of carriers may well explain the decoupling of electrical conductivity and Seebeck coefficient and their simultaneous enhancements in the thermo-electro-magnetic flexible films.
View Article and Find Full Text PDFJ Comput Chem
January 2025
Department of Chemistry, Gottwald Center for the Sciences, University of Richmond, Richmond, Virginia, USA.
The energies and geometries of the lowest lying singlet and triplet states of the four diradicals formed by removing two H atoms from thiophene have been characterized. We utilized the highly correlated, multireference methods configuration interaction with single and double excitations with and without the Pople correction for size-extensivity (MR-CISD+Q and MR-CISD) and averaged quadratic coupled cluster theory (MR-AQCC). CAS (8,7) and CAS (10,8) active spaces involving σ, σ*, π, and π* orbitals were employed along with the cc-pVDZ and cc-pVTZ basis sets.
View Article and Find Full Text PDFMater Horiz
January 2025
Institute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural University, Guangzhou, 510642, China.
Conversion of nitrogen (N) to ammonia (NH) is a significant process that occurs in environment and in the field of chemistry, but the traditional NH synthesis method requires high energy and pollutes the environment. In this work, the charge, orbital and spin order of the single-atom Fe loaded on heteroatom (X) doped-MoCS (X = B, N, O, F, P and Se) and its synergistic effect on electrochemical nitrogen reduction reaction (eNRR) were investigated using well-defined density functional theory (DFT) calculations. Results revealed that the X-element modified the charge loss capability of Fe atoms and thereby introduced a net spin through heteroatom doping, resulting in the magnetic moment modulation of Fe.
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