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Over the years, theoretical calculations and scalable computer simulations have complemented ultrafast experiments, as they offer the advantage of overcoming experimental restrictions and having access to the whole dynamics. This synergy between theory and experiment promises to yield a deeper understanding of photochemical processes, offering valuable insights into the behavior of complex systems at the molecular level. However, the ability of theoretical models to predict ultrafast experimental outcomes has remained largely unexplored. In this work, we aim to predict the electron diffraction signals of an upcoming ultrafast photochemical experiment using high-level electronic structure calculations and non-adiabatic dynamics simulations. In particular, we perform trajectory surface hopping with extended multi-state complete active space with second order perturbation simulations for understanding the photodissociation of cyclobutanone (CB) upon excitation at 200 nm. Spin–orbit couplings are considered for investigating the role of triplet states. Our simulations capture the bond cleavage after ultrafast relaxation from the 3s Rydberg state, leading to the formation of the previously observed primary photoproducts: CO + cyclopropane/propene (C3 products), ketene, and ethene (C2 products). The ratio of the C3:C2 products is found to be about 1:1. Within 700 fs, the majority of trajectories transition to their electronic ground state, with a small fraction conserving the initial cyclobutanone ring structure. We found a minimal influence of triplet states during the early stages of the dynamics, with their significance increasing at later times. We simulate MeV-ultrafast electron diffraction (UED) patterns from our trajectory results, linking the observed features with specific photoproducts and the underlying structural dynamics. Our analysis reveals highly intense features in the UED signals corresponding to the photochemical processes of CB. These features offer valuable insights into the experimental monitoring of ring opening dynamics and the formation of C3 and C2 photoproducts. [ABSTRACT FROM AUTHOR]

Excited atomic nitrogen atoms play an important role in plasma formation in hypersonic shock-waves, as happens during spacecraft reentry and other high velocity vehicle applications. In this study, we have thoroughly studied collision induced excitation associated with two colliding nitrogen atoms in the N(4S), N(2D), and N(2P) states at collision energies up to 6 eV, using time-independent scattering calculations to determine cross sections and temperature-dependent rate coefficients. The calculations are based on potential curves and couplings determined in earlier multireference configuration interaction calculations with large basis sets, and the results are in good agreement with experiments where comparisons are possible. To properly consider the spin–orbit coupling matrix, we have developed a scaling method for treating transitions between different fine-structure components that only require calculations with two coupled states, and with this, we define accurate degeneracy factors for determining cross sections and rate coefficients that include all states. The results indicate that both spin–orbit and derivative coupling effects can play important roles in collisional excitation and quenching, and that although derivative coupling is always much stronger than spin–orbit, there are many transitions where only spin–orbit can contribute. As part of this, we identify two distinct pathways associated with N(2P) relaxation and one Auger-like mechanism leading to two N(2D) that could be important at high temperatures. [ABSTRACT FROM AUTHOR]

In the present work, the electronic structure and chemical bonding of the MoC X3Σ− ground state and the six lowest excited states, A3Δ, a1Γ, b5Σ−, c1Δ, d1Σ+, and e5Π, have been investigated in detail using multireference configuration interaction methods and basis sets, including relativistic effective core potentials. In addition, scalar relativistic effects have been considered in the second order Douglas–Kroll–Hess approximation, while spin–orbit coupling has also been calculated. Five of the investigated states, X3Σ−, A3Δ, a1Γ, c1Δ, and d1Σ+, present quadruple σ2σ2π2π2 bonds. Experimentally, the predissociation threshold of MoC was measured using resonant two-photon ionization spectroscopy, allowing for a precise measurement of the dissociation energy of the ground state. Theoretically, the complete basis set limit of the calculated dissociation energy with respect to the atomic ground state products, including corrections for scalar relativistic effects, De(D0), is computed as 5.13(5.06) eV, in excellent agreement with our measured value of D0(MoC) of 5.136(5) eV. Furthermore, the calculated dissociation energies of the states having quadruple bonds with respect to their adiabatic atomic products range from 6.22 to 7.23 eV. The excited electronic states A3Δ2 and c1Δ2 are calculated to lie at 3899 and 8057 cm−1, also in excellent agreement with the experimental values of DaBell et al., 4002.5 and 7834 cm−1, respectively. [ABSTRACT FROM AUTHOR]

The interaction between the magnetic moment of an electron and the magnetic field generated by a moving charge is one component of the spin–orbit interaction. The nuclei in a molecule or solid are charged, are generally in vibrational motion, and so contribute to this interaction, but the direct coupling between nuclear momentum and electron spin is normally ignored in discussions of spin-forbidden phenomena such as transitions between states of different spin, even when the nuclei are recognized as playing a fundamental role (spin–vibronic coupling). Here, we investigate the spin–orbit interaction in a Heisenberg model interacting with vibrating point charges representing nearby bridging ligands. To reach the model, we apply second order perturbation theory to the Hubbard model with the spin–orbit interaction. In contrast to the other components of the spin–orbit interaction, the part that directly couples the momentum of the charge and electron spin appears at first order as an effective magnetic field at each site. We find that the inclusion of this nuclear-motion induced spin–orbit coupling can increase the rate of otherwise spin-forbidden transitions between different spin states of the Heisenberg model by many orders of magnitude. This overlooked interaction may, therefore, play a significant role in spin-forbidden phenomena such as spin relaxation in coupled spin-qubits. [ABSTRACT FROM AUTHOR]

Investigating the interplay between charge and spin conversion in two-dimensional (2D) materials holds significant promise for futuristic electronic applications. Through density functional theory, our study delves into the charge-spin conversion and spin density dynamics in the non-magnetic SnNBr monolayer under time-reversal invariance. The breaking of out-of-plane mirror symmetry and inversion symmetry, along with the presence of spin–orbit coupling (SOC) lead to a notable momentum-dependent spin band splitting or Rashba effect induced by the inherent out-of-plane electric field. Theoretical calculations reveal not only the presence of profound Rashba spin splitting but also the coexistence of intrinsic spin Hall effects in the SnNBr monolayer. Analysis of k-resolved spin Berry curvature sheds light on the origin of the substantial intrinsic spin Hall conductivity. Furthermore, our research highlights the modulation of charge-to-spin conversion and spin density accumulation through in-plane biaxial strains. Moreover, the variation in the Rashba parameter is correlated with the changes in the built-in out-of-plane electric field and microscopic atomic orbital contributions. These findings underscore the exceptional potential of the non-centrosymmetric SnNBr monolayer for advanced spintronics, spin-orbitronics, and piezo-spintronic applications, and serve as a catalyst for further experimental investigations. [ABSTRACT FROM AUTHOR]

A relativistic magnetic hyperfine interaction Hamiltonian based on the Douglas–Kroll–Hess (DKH) theory up to the second order is implemented within the ab initio multireference methods, including spin–orbit coupling in the Molcas/OpenMolcas package. This implementation is applied to calculate relativistic hyperfine coupling (HFC) parameters for atomic systems and diatomic radicals with valence s or d orbitals by systematically varying active space size in the restricted active space self-consistent field formalism with restricted active space state interaction for spin–orbit coupling. The DKH relativistic treatment of the hyperfine interaction reduces the Fermi contact contribution to the HFC due to the presence of kinetic factors that regularize the singularity of the Dirac delta function in the nonrelativistic Fermi contact operator. This effect is more prominent for heavier nuclei. As the active space size increases, the relativistic correction of the Fermi contact contribution converges well to the experimental data for light and moderately heavy nuclei. The relativistic correction, however, does not significantly affect the spin-dipole contribution to the hyperfine interaction. In addition to the atomic and molecular systems, the implementation is applied to calculate the relativistic HFC parameters for large trivalent and divalent Tb-based single-molecule magnets (SMMs), such as Tb(III)Pc2 and Tb(II) ( C p iPr 5 ) 2 without ligand truncation using well-converged basis sets. In particular, for the divalent SMM, which has an unpaired valence 6s/5d hybrid orbital, the relativistic treatment of HFC is crucial for a proper description of the Fermi contact contribution. Even with the relativistic hyperfine Hamiltonian, the divalent SMM is shown to exhibit strong tunability of HFC via an external electric field (i.e., strong hyperfine Stark effect). [ABSTRACT FROM AUTHOR]

The Rashba spin–orbit coupling effect, primarily arising from structural-inversion asymmetry in periodic crystals, has garnered considerable attention due to its tunability and potential applications in spintronics. Its capability to manipulate electron spin without an external magnetic field opens new avenues for spintronic device design, particularly in semiconductor technology. Within this framework, 2D Rashba materials hold special interest due to their inherent characteristics, which facilitate miniaturization and engineering capabilities. In this Perspective article, we provide an overview of recent advancements in the research of 2D Rashba materials, aiming to offer a comprehensive understanding of the diverse manifestations and multifaceted implications of the Rashba effect in material science. Rather than merely presenting a list of materials, our approach involves synthesizing various viewpoints, assessing current trends, and addressing challenges within the field. Our objective is to bridge the gap between fundamental research and practical applications by correlating each material with the necessary advancements required to translate theoretical concepts into tangible technologies. Furthermore, we highlight promising avenues for future research and development, drawing from insights gleaned from the current state of the field. [ABSTRACT FROM AUTHOR]

The kinetic energy dependence of the title reaction is examined using guided ion beam tandem mass spectrometry. Because this reaction is spin-forbidden, crossings between octet and sextet hypersurfaces presumably must occur. Furthermore, Sm+ must transition from a 4f66s1 configuration in the reactant to 4f55d2 in order to have the orbital occupancy required to form the triple bond in SmO+ (6Δ). Despite being strongly exothermic (∼4 eV), the reaction proceeds with low efficiency (18% ± 4%) via a barrierless process at low energies. Below ∼0.3 eV, the cross section follows a kinetic energy dependence that roughly parallels that of the collision rate for ion–dipole reactions. At higher collision energies, the reaction cross section increases until it follows the trajectory cross section closely from 3 to 5 eV, indicating that another pathway opens on the reaction hypersurface. Modeling this increase yields a threshold energy for this new pathway at 0.54 ± 0.05 eV. Theoretical potential energy surfaces that do not include spin–orbit interactions for the reaction show that there is a barrier of height 1.19 eV (MP2) or 0.49 eV [CCSD(T)] to insertion of Sm+ into the N2–O bond and that there are several places where octet and sextet surfaces can intersect and interact. By considering the distribution of spin–orbit states generated in the ion source, the internal energy of the N2O reactant, and the influence of coupling between electronic, orbital, and rotational angular momentum, the low-efficiency, exothermic behavior as well as the increase in efficiency at higher energies can plausibly be explained. [ABSTRACT FROM AUTHOR]

Rovibrational levels of low-lying electronic states of the gas-phase, diatomic molecules, PtH+ and PtH−, are computed on potential-energy functions obtained by using a hybrid spin–orbit configuration-interaction procedure. PtH− has a well-separated Σ 0 + + 1 ground state, while the first two electronic states of PtH+ ( Σ 0 + + 1 and 3Δ3) are nearly degenerate. Combining the experimental photoelectron (PE) spectra of PtH− with theoretical photodetachment spectroscopy leads to an improved value for the electron affinity of PtH, EA(PtH) = (1.617 ± 0.015) eV. When PtH− is a product of photodissociation of PtHCO2−, its PE spectrum is broad because of rotational excitation. Temperature-dependent thermodynamic functions and thermochemistry of dissociation are computed from the theoretical energy levels. Previously published energetic quantities for PtH+ and PtH− are revised. The ground 1Σ+ term of PtH+ is not well described using single-reference theory. [ABSTRACT FROM AUTHOR]

Chirality ubiquitously appears in nature; however, its quantification remains obscure owing to the lack of microscopic description at the quantum-mechanical level. We propose a way of evaluating chirality in terms of the electric toroidal monopole, a practical entity of time-reversal even pseudoscalar (parity-odd) objects reflecting relevant electronic wave functions. For this purpose, we analyze a twisted methane molecule at the quantum-mechanical level, showing that the electric toroidal monopoles become a quantitative indicator for chirality. In the twisted methane, we clarify that the handedness of chirality corresponds to the sign of the expectation value of the electric toroidal monopole and that the most important ingredient is the modulation of the spin-dependent imaginary hopping between the hydrogen atoms, while the relativistic spin–orbit coupling within the carbon atom is irrelevant for chirality. [ABSTRACT FROM AUTHOR]

Spin–orbit coupling induces a current density in the ground state, which consequently requires a generalization for meta-generalized gradient approximations. That is, the exchange–correlation energy has to be constructed as an explicit functional of the current density, and a generalized kinetic energy density has to be formed to satisfy theoretical constraints. Herein, we generalize our previously presented formalism of spin–orbit current density functional theory [Holzer et al., J. Chem. Phys. 157, 204102 (2022)] to non-magnetic and magnetic periodic systems of arbitrary dimension. In addition to the ground-state exchange–correlation potential, analytical derivatives such as geometry gradients and stress tensors are implemented. The importance of the current density is assessed for band gaps, lattice constants, magnetic transitions, and Rashba splittings. In the latter, the impact of the current density may be larger than the deviation between different density functional approximations. [ABSTRACT FROM AUTHOR]

In recent years, magnetic skyrmion-based spin-torque nano-oscillators (STNOs) have attracted considerable interest for their prospect in future-generation communication and spintronic technologies. However, some critical issues, which hamper their practical applications, e.g., the long start-up time and variable skyrmion gyration orbit, remain to be resolved. Here, we numerically demonstrate the realization of a fixed-orbit STNO, which is based on an interlayer-coupled meron–skyrmion (MS) pair instead of a magnetic skyrmion. In this STNO, the MS pair possesses a structurally defined, fixed orbit within a broad range of driving currents, even in the presence of random defects. The output frequency range of the STNO based on an MS pair far exceeds that of the STNO typically featuring a single skyrmion. Moreover, the output frequency of this STNO can be further elevated if more MS pairs are incorporated. Our results reveal the nontrivial dynamics of the interlayer-coupled MS pair, opening perspectives for the design and optimization of fundamental spintronic devices. [ABSTRACT FROM AUTHOR]

Rovibrational levels of low-lying electronic states of the gas-phase, diatomic molecules, PtH+ and PtH−, are computed on potential-energy functions obtained by using a hybrid spin–orbit configuration-interaction procedure. PtH− has a well-separated Σ 0 + + 1 ground state, while the first two electronic states of PtH+ ( Σ 0 + + 1 and 3Δ3) are nearly degenerate. Combining the experimental photoelectron (PE) spectra of PtH− with theoretical photodetachment spectroscopy leads to an improved value for the electron affinity of PtH, EA(PtH) = (1.617 ± 0.015) eV. When PtH− is a product of photodissociation of PtHCO2−, its PE spectrum is broad because of rotational excitation. Temperature-dependent thermodynamic functions and thermochemistry of dissociation are computed from the theoretical energy levels. Previously published energetic quantities for PtH+ and PtH− are revised. The ground 1Σ+ term of PtH+ is not well described using single-reference theory. [ABSTRACT FROM AUTHOR]

The kinetic energy dependence of the title reaction is examined using guided ion beam tandem mass spectrometry. Because this reaction is spin-forbidden, crossings between octet and sextet hypersurfaces presumably must occur. Furthermore, Sm+ must transition from a 4f66s1 configuration in the reactant to 4f55d2 in order to have the orbital occupancy required to form the triple bond in SmO+ (6Δ). Despite being strongly exothermic (∼4 eV), the reaction proceeds with low efficiency (18% ± 4%) via a barrierless process at low energies. Below ∼0.3 eV, the cross section follows a kinetic energy dependence that roughly parallels that of the collision rate for ion–dipole reactions. At higher collision energies, the reaction cross section increases until it follows the trajectory cross section closely from 3 to 5 eV, indicating that another pathway opens on the reaction hypersurface. Modeling this increase yields a threshold energy for this new pathway at 0.54 ± 0.05 eV. Theoretical potential energy surfaces that do not include spin–orbit interactions for the reaction show that there is a barrier of height 1.19 eV (MP2) or 0.49 eV [CCSD(T)] to insertion of Sm+ into the N2–O bond and that there are several places where octet and sextet surfaces can intersect and interact. By considering the distribution of spin–orbit states generated in the ion source, the internal energy of the N2O reactant, and the influence of coupling between electronic, orbital, and rotational angular momentum, the low-efficiency, exothermic behavior as well as the increase in efficiency at higher energies can plausibly be explained. [ABSTRACT FROM AUTHOR]

Understanding excited-state intramolecular proton transfer (ESIPT) is essential for designing organic molecules to enhance photophysical and luminophore properties in the development of optoelectronic devices. In this context, an attempt has been made to understand the impact of substituents on the ESIPT process of 2-(oxazolinyl)-phenol. Electron donating (EDG: –NH2, –OCH3, and –CH3) and electron withdrawing (EWG: –Cl, –Br, –COOH, –CF3, –CN, and –NO2) substitutions have been computationally designed and screened through density functional theory (DFT) and time-dependent density-functional theory (TDDFT) calculations. Furthermore, the ground state intramolecular proton transfer and ESIPT mechanisms of these designed luminophores are explored using the transition state theory. The results reveal that molecules with EDG show higher absorption and emission peaks than molecules with EWG and also indicate that the mobility of charge carriers in 2-(oxazolinyl)-phenol derivatives is significantly influenced by substituents. We found that the EWGs decrease the reorganization energy and increase the vertical ionization potential and electron affinity values, as well as the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, compared to the EDG substituted molecules. Significantly, the excited state (S1) of the keto emission (K) form shows notably larger values for the EDG substitutions. The intersystem crossing pathway efficiency weakens with reduced spin–orbit coupling matrix element in the enol form with electron-donating substituents and vice versa in the keto form during S1–T3 transitions. Our research links intramolecular proton transfers and triplet generation, making these substituted molecules appealing for optoelectronic devices. Introducing EDGs, such as –NH2, boosts the ESIPT reaction in 2-(oxazolinyl)-phenol. This study guides designing ESIPT emitters with unique photophysical properties. [ABSTRACT FROM AUTHOR]

The interaction of electronic spin and molecular vibrations mediated by spin–orbit coupling governs spin relaxation in molecular qubits. We derive an extended molecular spin Hamiltonian that includes both adiabatic and non-adiabatic spin-dependent interactions, and we implement the computation of its matrix elements using state-of-the-art density functional theory. The new molecular spin Hamiltonian contains a novel spin–vibrational orbit interaction with a non-adiabatic origin, together with the traditional molecular Zeeman and zero-field splitting interactions with an adiabatic origin. The spin–vibrational orbit interaction represents a non-Abelian Berry curvature on the ground-state electronic manifold and corresponds to an effective magnetic field in the electronic spin dynamics. We further develop a spin relaxation rate model that estimates the spin relaxation time via the two-phonon Raman process. An application of the extended molecular spin Hamiltonian together with the spin relaxation rate model to Cu(II) porphyrin, a prototypical S = 1/2 molecular qubit, demonstrates that the spin relaxation time at elevated temperatures is dominated by the non-adiabatic spin–vibrational orbit interaction. The computed spin relaxation rate and its magnetic field orientation dependence are in excellent agreement with experimental measurements. [ABSTRACT FROM AUTHOR]

A diabatic potential energy matrix (DPEM) for the two lowest states of BeH 2 + has been constructed using the combined-hyperbolic-inverse-power-representation (CHIPR) method. By imposing symmetry constraints on the coefficients of polynomials, the complete nuclear permutation inversion symmetry is correctly preserved in the CHIPR functional form. The symmetrized CHIPR functional form is then used in the diabatization by ansatz procedure. The ab initio energies are reproduced with satisfactory accuracy. In addition, the CHIPR-based DPEM also reproduces the local topology of a conical intersection. Future work will focus on a complete four-state diabatic representation with emphasis on the long-range interactions and spin–orbit couplings, which will enable accurate quantum scattering calculations for the Be+(2P) + H2 → BeH+(X1Σ+) + H(2S) reaction. [ABSTRACT FROM AUTHOR]

Multi-reference configuration interaction potential energy curves (PECs) and spin–orbit couplings for the X 2Π, A 2Σ+, 1 2Σ−, 1 4Σ−, and 1 4Π states of OH are computed and refined against empirical energy levels and transitions to produce a spectroscopic model. Predissociation lifetimes are determined by discretizing continuum states in the variational method nuclear motion calculation by restricting the calculation to a finite range of internuclear separations. Varying this range gives a series of avoided crossings between quasi-bound states associated with the A 2Σ+ and continuum states, from which predissociation lifetimes are extracted. 424 quasi-bound A 2Σ+ state rovibronic energy levels are analyzed, and 374 predissociation lifetimes are produced, offering good coverage of the predissociation region. Agreement with measured lifetimes is satisfactory, and a majority of computed results were within experimental uncertainty. A previously unreported A 2Σ+ state predissociation channel that goes via X 2Π is identified in the calculations. A Python package, binSLT, produced to calculate predissociation lifetimes, associated line broadening parameters, and lifetime uncertainties is made available. The PECs and other curves from this work will be used to produce a rovibronic ExoMol line list and temperature-dependent photodissociation cross sections for the hydroxyl radical. [ABSTRACT FROM AUTHOR]

Chiral molecules can exhibit strong spin–orbit coupling, which can result in a large spin polarization. This is due to the fact that the energy levels of the electrons in a chiral molecule are strongly influenced by the chiral structure of the molecule, which can result in the separation of the energy levels for electrons with different spin orientations. We report a controlled spin-selective transmission of electrons through 20 base-paired poly-cytosine molecules functionalized with MoS2 flakes on ITO glass via the quantum mechanical tunneling effect. A reversion in spin polarization was observed after the silver ions interact with poly-cytosine due to the strong coordination of Ag(I) with cytosine–cytosine (C–C) mismatches, indicating the formation of duplex structural motifs, as confirmed by the circular dichroism spectroscopy at room temperature. Manipulating the spin of an electron through such a small molecule merely controlled by special cations could pave the way for major advances in spin-independent charge transport, advanced bioanalytical system design, and related applications. [ABSTRACT FROM AUTHOR]

Chiral molecules can exhibit strong spin–orbit coupling, which can result in a large spin polarization. This is due to the fact that the energy levels of the electrons in a chiral molecule are strongly influenced by the chiral structure of the molecule, which can result in the separation of the energy levels for electrons with different spin orientations. We report a controlled spin-selective transmission of electrons through 20 base-paired poly-cytosine molecules functionalized with MoS2 flakes on ITO glass via the quantum mechanical tunneling effect. A reversion in spin polarization was observed after the silver ions interact with poly-cytosine due to the strong coordination of Ag(I) with cytosine–cytosine (C–C) mismatches, indicating the formation of duplex structural motifs, as confirmed by the circular dichroism spectroscopy at room temperature. Manipulating the spin of an electron through such a small molecule merely controlled by special cations could pave the way for major advances in spin-independent charge transport, advanced bioanalytical system design, and related applications. [ABSTRACT FROM AUTHOR]

We investigate the native point defects in the long-wavelength infrared (LWIR) detector material H g 0.75 C d 0.25 Te using a dielectric-dependent hybrid density functional combined with spin–orbit coupling. Characterizing these point defects is essential as they are responsible for intrinsic doping and nonradiative recombination centers in the detector material. The dielectric-dependent hybrid functional allows for an accurate description of the bandgap (E g) for Hg 1 − x Cd x Te (MCT) over the entire compositional range, a level of accuracy challenging with standard hybrid functionals. Our comprehensive examination of the native point defects confirms that cation vacancies V Hg (Cd) are the primary sources of p -type conductivity in the LWIR material given their low defect formation energies and the presence of a shallow acceptor level (− /0) near the valence-band maximum. In addition to the shallow acceptor level, the cation vacancies exhibit a deep charge transition level (2 − / −) situated near the midgap, characteristic of nonradiative recombination centers. Our results indicate that Hg interstitial could also be a deep center in the LWIR MCT through a metastable configuration under the Hg-rich growth conditions. While an isolated Te antisite does not show deep levels, the formation of V Hg –Te Hg defect complex introduces a deep acceptor level within the bandgap. [ABSTRACT FROM AUTHOR]

The combined influence of spin–orbit coupling and spatial inversion asymmetry leads to an enhancement of electronic properties, including Rashba spin-splittings as well as spin Hall effect. Recent research has shown the possibility to create two-dimensional Janus materials with inherent structural asymmetry. In this work, the structural stability, piezoelectricity, electronic properties, and intrinsic spin Hall conductivity of quintuple-layer atomic Janus Sb2XSX' (X, X' = S, Se, Te; X ≠ X') monolayers are investigated using first-principles calculations within the framework of density functional theory. They demonstrate relatively high in-plane piezoelectric coefficients ( d 22) and also possess out-of-plane piezoelectric coefficients ( d 31), which is due to the breaking of inversion symmetry in the crystal structure with the space group P3m1. Large Rashba parameters are obtained in Janus Sb2XSX' monolayers, especially high for Sb 2 S 2 Te (1.62 eV Å) and Sb 2 SeSTe (1.33 eV Å) due to strong spin–orbit coupling. Moreover, Rashba-like spin-splitting is also observed in the edge-states as well, which is highest for Sb 2 SeSTe with 2.17 eV Å. Furthermore, Sb 2 S 2 Te and Sb 2 SeSTe monolayers reveal a significantly high Berry curvature (65.59 and 61.05 Bohr 2), spin Berry curvature (− 118.4 and − 120.6 Bohr 2), and spin Hall conductivity (1.8 and 1.6 e 2 /h). Our results suggest that Janus Sb 2 S 2 Te and Sb 2 SeSTe monolayers could be an excellent platform for multifunctional electronic applications. [ABSTRACT FROM AUTHOR]

N-heterocyclic carbene (NHC) iridium(III) complexes are considered as promising candidates for blue emitters in organic light-emitting diodes. They can play the roles of the emitter as well as of electron and hole transporters in the same emission layer. We investigate optical transitions in such complexes with account of geometry and electronic structure changes upon excitation or charging and exciton transfer between the complexes from first principles. It is shown that excitation of NHC iridium complexes is accompanied by a large reorganization energy ∼0.7 eV and a significant loss in the oscillator strength, which should lead to low exciton diffusion. Calculations with account of spin–orbit coupling reveal a small singlet–triplet splitting ∼0.1 eV, whereas the oscillator strength for triplet excitations is found to be an order of magnitude smaller than for the singlet ones. The contributions of the Förster and Dexter mechanisms are analyzed via the explicit integration of transition densities. It is shown that for typical distances between emitter complexes in the emission layer, the contribution of the Dexter mechanism should be negligible compared to the Förster mechanism. At the same time, the ideal dipole approximation, although giving the correct order of the exciton coupling, fails to reproduce the result taking into account spatial distribution of the transition density. For charged NHC complexes, we find a number of optical transitions close to the emission peak of the blue emitter with high exciton transfer rates that can be responsible for exciton–polaron quenching. The nature of these transitions is analyzed. [ABSTRACT FROM AUTHOR]

Transition metal oxides (TMOs) demonstrate a broad spectrum of properties encompassing electronic correlations, anisotropic transport, magnetism, and optical behavior. The anisotropy arises from both intrinsic crystal symmetry and extrinsic factors like epitaxial strain and structural asymmetry at TMO interfaces. Weiss and Neel's work has elucidated anisotropic magnetic behavior in antiferromagnetic (AFM) materials. AFM TMOs exhibit unique magnetotransport behavior, including weak antilocalization (WAL) and anisotropic magnetoresistance (AMR). Understanding the magnetic structure and band topology in AFM perovskites and their interfaces enables the tailored design of materials for spintronics and energy conversion. In few interfaces lacking inversion symmetry, Rashba spin–orbit coupling (SOC) induces WAL, a quantum correction in conductivity in a two-dimensional electronic system. Electron accumulation and charge transfer across 3d, 5d transition metal-based perovskite interfaces affect WAL and AMR, as observed in 3d/3d and 3d/5d AFM heterostructures, respectively. Advancements in spintronics rely on exploring spin-dependent transport anisotropy. This review focuses on various scattering mechanisms, categorized as extrinsic and intrinsic, in anisotropic transport, particularly in 3d/5d AFM superlattices. The WAL scattering mechanism depends on both intrinsic factors related to Rashba SOC-induced band topology and extrinsic sources like spin impurities and lattice ions. Moreover, the investigation into AMR mechanisms involves the application of impurity-based extrinsic scattering models, which are aligned with the Rashba and Dresselhauss models on Fermi surfaces. This exploration specifically targets the interface of two-band insulators, exemplified by LaAlO3/SrTiO3 and LaVO3/KTaO3. Furthermore, this model achieves comprehensive coverage, extending its applicability to 3d/5d AFM heterostructures like LaMnO3/SrIrO3 and CaMnO3/CaIrO3. Additionally, the intrinsic scattering mechanism tied to Berry phase effects related to band topology is studied, focusing on the CaMnO3/CaIrO3 superlattice. Despite manipulation challenges stemming from reduced stray fields, AFM materials show potential in interface physics and applications within the realm of spintronics. [ABSTRACT FROM AUTHOR]

Bromine atom (Br) reactions lead to ozone depletion in the troposphere and stratosphere. Photodegradation of bromocarbons is one of the main sources of bromine atoms in the atmosphere. Here, we use high-level ab initio methods, including spin–orbit effects, to study the photodissociation of the CH2Br radical. All possible fragmentation pathways, namely CH2Br + hν → CH2 + Br, HCBr + H, and CBr + H2, have been analyzed. Potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distance of each pathway have been calculated. Considering the actinic fluxes of solar irradiation in the troposphere and in the stratosphere in the relevant range of frequencies, it is found that the first five excited states of CH2Br can be accessed from the ground state. Analysis of the potential curves shows that the pathways producing CH2 + Br and HCBr + H can proceed through a fast direct dissociation mechanism, while the pathway leading to CBr + H2 involves much slower dissociation mechanisms like internal conversion between electronic states, predissociation, or tunneling through exit barriers. The main implications are that the two faster channels are predicted to be dominant, and the slower pathway is expected to be less relevant. The tropospheric and stratospheric solar actinic fluxes also allow for further dissociation of the HCBr and CBr fragments, generating additional Br atoms, provided that they survive possible collisions with other atmospheric reagents. Finally, we discuss the possible effect of each of the three CH2Br dissociation pathways on the depletion of atmospheric ozone. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) piezoelectric nanomaterials have widely been studied recently due to their promise for various applications in technology. Investigation of vertical piezoelectricity will contribute to a deeper understanding of the intrinsic mechanism of piezoelectric effects in the 2D structures. In this paper, we report a first-principle study for the structural, electronic, piezoelectric, and transport properties of new-designed Janus WSi Z 3 H (Z = N, P, and As) monolayers. The structural stability of WSi Z 3 H is theoretically confirmed based on the energetic, phonon dispersion, and also elastic analyses. At the ground state, while WSiN 3 H is an indirect semiconductor, both WSiP 3 H and WSiAs 3 H are predicted to be direct semiconductors with smaller bandgaps. When the spin-orbit coupling effects are taken into account, a large valley spin splitting is observed at the K point of WSi Z 3 H materials. Interestingly, a giant Rashba spin splitting is found in WSiP 3 H and WSiAs 3 H with Rashba constant α R up to 770.91 meV Å. Additionally, our first-principles study indicates that Janus WSi Z 3 H monolayers are piezoelectric semiconductors with high out-of-plane piezoelectric coefficient | d 31 | , up to 0.15 pm/V, due to the broken mirror symmetry. Besides, with high electron mobilities and also possessing direct band gaps, WSiP 3 H and WSiAs 3 H monolayers are favorable for applications in optoelectronics. [ABSTRACT FROM AUTHOR]

The Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach is a method to generate fully coupled diabatic potential energy surfaces (PESs) including relativistic effects, especially spin–orbit coupling. The spin–orbit coupling of a full molecule is determined only by the atomic states of selected relativistically treated atoms. The full molecular coupling effect is obtained by a diabatization with respect to asymptotic states, resulting in the correct geometry dependence of the spin–orbit effect. The ERCAR approach has been developed over the last decade and initially only for molecules with a single relativistic atom. This work presents its extension to molecules with more than a single relativistic atom using the iodine molecule as a proof-of-principle example. The theory for the general multiple atomic ERCAR approach is given. In this case, the diabatic basis is defined at the asymptote where all relativistic atoms are separated from the remaining molecular fragment. The effective spin–orbit operator is then a sum of spin–orbit operators acting on isolated relativistic atoms. PESs for the iodine molecule are developed within the new approach and it is shown that the resulting fine structure states are in good agreement with spin–orbit ab initio calculations. [ABSTRACT FROM AUTHOR]

Spin–orbit torque provides an efficient strategy for electric manipulation of magnetization. However, Joule heat accompanying with electron motion in the electron-mediated spin current result in unavoidable power dissipation. Moreover, the spin diffusion length in electron-mediated spin current is relatively short, preventing the transmission of spin information over long distances. Magnon-mediated spin current, without moving electrons, can be an excellent alternative to the conventional spin current. Magnon-mediated transfer torque effect has been reported in several previous works. Here, we report the magnon-mediated spin Hall magnetoresistance (SMR) and unidirectional magnetoresistance (UMR) in Pt/NiO/NiFe structures. The significant SMR and UMR were observed in the samples with the NiO thickness up to 60 nm, demonstrating the efficient transmission of magnon-mediated spin current over long distances in the NiO layer. In addition, we observed current-induced in-plane magnetization switching in the NiFe layer via the UMR measurement. These results demonstrated the possibility for developing the efficient spintronic devices operated by magnons. [ABSTRACT FROM AUTHOR]

Based on first-principles calculations, the current study deeply explores the thermoelectric properties of the Zintl compound SrPdTe. We found that the anharmonic vibration of Pd atoms plays an important role in the quartic anharmonic effect and the temperature dependence of the thermal conductivity. In the crystalline structure, Sr atoms form octahedra with eight surrounding Te atoms, while Pd atoms are located in the gaps between the octahedra. This structure makes the strong atomic mean square displacement of Pd atoms the main factor leading to the ultralow thermal conductivity. The study also reveals the effects of phonon frequency renormalization and four-phonon scattering on heat transfer performance. Even considering the spin–orbit coupling effect, multiple secondary valence band tops maintain the power factor of the material at high temperatures, providing a potential opportunity for achieving excellent thermoelectric performance. [ABSTRACT FROM AUTHOR]

Metal-halide perovskites are a structurally, chemically, and electronically diverse class of semiconductors with applications ranging from photovoltaics to radiation detectors and sensors. Understanding neutral electron–hole excitations (excitons) is key for predicting and improving the efficiency of energy-conversion processes in these materials. First-principles calculations have played an important role in this context, allowing for a detailed insight into the formation of excitons in many different types of perovskites. Such calculations have demonstrated that excitons in some perovskites significantly deviate from canonical models due to the chemical and structural heterogeneity of these materials. In this Perspective, I provide an overview of calculations of excitons in metal-halide perovskites using Green's function-based many-body perturbation theory in the GW + Bethe–Salpeter equation approach, the prevalent method for calculating excitons in extended solids. This approach readily considers anisotropic electronic structures and dielectric screening present in many perovskites and important effects, such as spin–orbit coupling. I will show that despite this progress, the complex and diverse electronic structure of these materials and its intricate coupling to pronounced and anharmonic structural dynamics pose challenges that are currently not fully addressed within the GW + Bethe–Salpeter equation approach. I hope that this Perspective serves as an inspiration for further exploring the rich landscape of excitons in metal-halide perovskites and other complex semiconductors and for method development addressing unresolved challenges in the field. [ABSTRACT FROM AUTHOR]

We demonstrate that, for systems with spin–orbit coupling and an odd number of electrons, the standard fewest switches surface hopping algorithm does not conserve the total linear or angular momentum. This lack of conservation arises not so much from the hopping direction (which is easily adjusted) but more generally from propagating adiabatic dynamics along surfaces that are not time reversible. We show that one solution to this problem is to run along eigenvalues of phase-space electronic Hamiltonians H(R, P) (i.e., electronic Hamiltonians that depend on both nuclear position and momentum) with an electronic–nuclear coupling Γ · P [see Eq. (25)], and we delineate the conditions that must be satisfied by the operator Γ. The present results should be extremely useful as far as developing new semiclassical approaches that can treat systems where the nuclear, electronic orbital, and electronic spin degrees of freedom altogether are all coupled together, hopefully including systems displaying the chiral-induced spin selectivity effect. [ABSTRACT FROM AUTHOR]

In this work, we have studied the spin-dependent ballistic transport and anomalous quantum tunneling in bilayer graphene horizontally placed in between two Rashba–Zeeman (RZ) leads under external electric biasing. We investigated the transmission and conductance for the proposed system using scattering matrix formalism and the Landauer–Büttiker formula considering a double delta-like barrier under a set of experimentally viable parameters. We found that the transmission characteristics are notably different for up- and down-spin incoming electrons depending upon the strength of magnetization. Moreover, the transmission of up- and down-spin electrons is found to be magnetization orientation dependent. The maximum tunneling conductance can be achieved by tuning biasing energy and magnetization strength and choosing a material with suitable Rashba spin–orbit coupling (RSOC). This astonishing property of our system can be utilized in fabricating devices, such as spin filters. We found that the Fano factor of our system is 0.4 under strong magnetization conditions, while it reduces to 0.3 under low magnetization conditions. Moreover, we also noticed that the transmission and conductance significantly depend on the Rashba–Zeeman effect. Therefore, considering a suitable RZ material, the tunneling of the electrons can be tuned and controlled. Our result suggests that considering suitable strength and orientation of magnetization with moderate RSOC, one can obtain a different transmission probability for spin species under suitable biasing energy. These results indicate the suitability of the proposed system in fabrication of spintronic devices, such as spin filter, spin transistor, etc. [ABSTRACT FROM AUTHOR]

Although it plays a critical role in the photophysics and catalysis of lanthanides, spin–orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin–orbit multiconfiguration second-order quasi-degenerate perturbation theory. The energies of six ionization transitions are precisely measured; the adiabatic ionization energy of the neutral cluster is 38 045 (5) cm−1. Most of the electronic states involved in these transitions are identified as spin–orbit coupled states consisting of two or more electron spins. The electron configurations of these states are 4f46s2 for the neutral cluster and 4f46s for the singly charged cation, both in planar rhombus-type structures. The spin–orbit splitting due to the coupling of the electrons on the separate Pr atoms is on the order of hundreds of wavenumbers. [ABSTRACT FROM AUTHOR]

The scattering of H by I is a prototypical model system for light-heavy scattering in which relativistic coupling effects must be taken into account. Scattering calculations depend strongly on the accuracy of the potential energy surface (PES) model. The methodology to obtain such an accurate PES model suitable for scattering calculations is presented, which includes spin–orbit (SO) coupling within the Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach. In this approach, the SO coupling is determined only for the atomic states of the heavy atom, and the geometry dependence of the SO effect is accounted for by a diabatization with respect to asymptotic states. The accuracy of the full model, composed of a Coulomb part and the SO model, is achieved in the following ways. For the SO model, the extended ERCAR approach is applied, which accounts for both intra-state and inter-state SO coupling, and an extended number of diabatic states are included. The corresponding coupling constants for the SO operator are obtained from experiments, which are more accurate than computed values. In the Coulomb Hamiltonian model, special attention is paid to the long range behavior and accurate c6 dispersion coefficients. The flexibility and accuracy of this Coulomb model are achieved by combining partial models for three different regions. These are merged via artificial neural networks, which also refine the model further. In this way, an extremely accurate PES model for hydrogen iodide is obtained, suitable for accurate scattering calculations. [ABSTRACT FROM AUTHOR]

A first implementation of analytic gradients for spinor-based relativistic equation-of-motion coupled-cluster singles and doubles method using an exact two-component Hamiltonian augmented with atomic mean-field spin–orbit integrals is reported. To demonstrate its applicability, we present calculations of equilibrium structures and harmonic vibrational frequencies for the electronic ground and excited states of the radium mono-amide molecule (RaNH2) and the radium mono-methoxide molecule (RaOCH3). Spin–orbit coupling is shown to quench Jahn–Teller effects in the first excited state of RaOCH3, resulting in a C3v equilibrium structure. The calculations also show that the radium atoms in these molecules serve as efficient optical cycling centers. [ABSTRACT FROM AUTHOR]

Pseudopotentials (PP) are extensively used in electronic structure calculations, particularly for molecules containing heavy elements. Parameters in PPs are mainly determined from ab initio results, and errors of such PPs in density functional theory (DFT) calculations have been studied previously. However, PP errors on results with spin–orbit coupling and those in time-dependent DFT (TDDFT) calculations have not been reported previously. In this work, we investigate the error of the small-core energy-consistent Stuttgart/Koln pseudopotentials in DFT and TDDFT calculations with and without spin–orbit coupling. Ground state bond lengths, harmonic frequencies, dissociation energies, and vertical excitation energies for a series of closed-shell diatomic heavy and superheavy p-block molecules are calculated using several popular exchange-correlation functionals. PP errors are estimated by comparing with results using the all-electron Dirac–Coulomb (-Gaunt) Hamiltonian. Our results show that the difference between ground state properties and most excitation energies in scalar-relativistic calculations with the PP and those of all-electron calculations is quite small. This difference becomes somewhat larger when spin–orbit coupling (SOC) is present, especially for properties that are affected by SOC to some extent. In addition, the errors of the PPs are insensitive to the employed exchange-correlation functionals in most cases. Our results indicate that reasonable DFT and TDDFT results can be obtained using the small-core energy-consistent Stuttgart/Koln pseudopotentials for heavy and super-heavy p-block molecules. [ABSTRACT FROM AUTHOR]

In connection to the chiral-induced spin selectivity effect, we theoretically analyze the electronic and spin states of edges of a finite p-orbital helical atomic chain with the intra-atomic spin–orbit interaction. This model can host the spin-filtering state in which two up-spins propagate in one direction and two down-spins propagate in the opposite direction without breaking the time-reversal symmetry (TRS). The enhancement of charge modulations concentrated at the edges due to the evanescent states is induced, although the spin density is absent because of the TRS. A Zeeman field at an edge of the atomic chain, which breaks the TRS, yields a finite spin polarization, whose direction depends on the chirality of the molecule. The chirality change induces a reasonable amount of the energy difference, which may provide an insight into the enantioselective adsorption of chiral molecules on the ferromagnetic surface. [ABSTRACT FROM AUTHOR]

Antiferromagnetic spintronics is intrigued due to its unique properties that could break through the restrictions in ferromagnets. A 3d/5d transition metal oxide heterostructure is a good platform in antiferromagnetic spintronics research since the strong spin–orbit coupling in 5d oxides may bring about delicate interaction with the correlation energy and motivate unconventional phenomena. Here, the transport and magnetic characters of bilayers composed of antiferromagnetic 3d perovskite NdNiO3 and 5d perovskite SrIrO3 were investigated. The decreased metal–insulator transition and Néel temperature associated with suppressed negative magnetoresistance, emerged spin-glass like phenomenon, and the humped nonlinear Hall effect were observed in NdNiO3/SrIrO3 bilayers, which were absent in NdNiO3 and SrIrO3 pure films. It suggests the important role of interfacial interaction between NdNiO3 and SrIrO3 in modulating heterostructure transport and magnetic behavior and also manifests that complex magnetic structures might be realized in NdNiO3/SrIrO3 bilayers. [ABSTRACT FROM AUTHOR]

We analyze from a theoretical perspective recent experiments where chiral discrimination in biological systems was established using Atomic Force Microscopy (AFM). Even though intermolecular forces involved in AFM measurements have different origins, i.e., electrostatic, bonding, exchange, and multipole interactions, the key molecular forces involved in enantiospecific biorecognition are electronic spin exchange and van der Waals (vdW) dispersion forces, which are sensitive to spin–orbit interaction (SOI) and space-inversion symmetry breaking in chiral molecules. The vdW contribution to chiral discrimination emerges from the inclusion of SOI and spin fluctuations due to the chiral-induced selectivity effect, a result we have recently demonstrated theoretically. Considering these two enantiospecific contributions, we show that the AFM results regarding chiral recognition can be understood in terms of a simple physical model that describes the different adhesion forces associated with different electron spin polarization generated in the (DD), (LL), and (DL) enantiomeric pairs, as arising from the spin part of the exchange and vdW contributions. The model can successfully produce physically reasonable parameters accounting for the vdW and exchange interaction strength, accounting for the chiral discrimination effect. This fact has profound implications in biorecognition where the relevant intermolecular interactions in the intermediate-distance regime are clearly connected to vdW forces. [ABSTRACT FROM AUTHOR]

In this paper, we explore the molecular basis of combining photodynamic therapy (PDT), a light-triggered targeted anticancer therapy, with the traditional chemotherapeutic properties of the well-known cytotoxic agent gemcitabine. A photosensitizer prerequisite is significant absorption of biocompatible light in the visible/near IR range, ideally between 600 and 1000 nm. We use highly accurate multiconfigurational CASSCF/MS-CASPT2/MM and TD-DFT methodologies to determine the absorption properties of a series of gemcitabine derivatives with the goal of red-shifting the UV absorption band toward the visible region and facilitating triplet state population. The choice of the substitutions and, thus, the rational design is based on important biochemical criteria and on derivatives whose synthesis is reported in the literature. The modifications tackled in this paper consist of: (i) substitution of the oxygen atom at O2 position with heavier atoms (O → S and O → Se) to red shift the absorption band and increase the spin–orbit coupling, (ii) addition of a lipophilic chain at the N7 position to enhance transport into cancer cells and slow down gemcitabine metabolism, and (iii) attachment of aromatic systems at C5 position to enhance red shift further. Results indicate that the combination of these three chemical modifications markedly shifts the absorption spectrum toward the 500 nm region and beyond and drastically increases spin–orbit coupling values, two key PDT requirements. The obtained theoretical predictions encourage biological studies to further develop this anticancer approach. [ABSTRACT FROM AUTHOR]

In this paper, we examined the effects of proximity-induced interactions such as Rashba spin-orbit coupling and effective Zeeman fields (EZFs) on the optical spectrum of n -type and p -type monolayer (ML)-MoS 2. The optical conductivity is evaluated using the standard Kubo formula under random-phase approximation by including the effective electron–electron interaction. It has been found that there exist two absorption peaks in n -type ML-MoS 2 and two knife shaped absorptions in p -type ML-MoS 2 , which are contributed by the inter-subband spin-flip electronic transitions within conduction and valence bands at valleys K and K ′ with a lifted valley degeneracy. The optical absorptions in n -type and p -type ML-MoS 2 occur in THz and infrared radiation regimes and the position, height, and shape of them can be effectively tuned by Rashba parameter, EZF parameters, and carrier density. The interesting theoretical predictions in this study would be helpful for the experimental observation of the optical absorption in infrared to THz bandwidths contributed by inter-subband spin-flip electronic transitions in a lifted valley degeneracy monolayer transition metal dichalcogenides system. The obtained results indicate that ML-MoS 2 with the platform of proximity interactions make it a promising infrared and THz material for optics and optoelectronics. [ABSTRACT FROM AUTHOR]

The recent discovery of inherently stable two-dimensional (2D) transition-metal dichalcogenides (TMDs) provides a unique platform for spintronic devices. However, its efficacy for electric detection by spin Hall magnetoresistance (SMR) has not been established yet. In this work, we report on SMR in 2D TMDs/ferromagnet heterostructures, i.e., PtSe 2 /NiFe (Py), whose magnitude reaches the maximum with bilayer PtSe 2. Notably, the SMR value in bilayer PtSe 2 /Py heterostructures undergoes a sign change with increasing Py thickness. For thinner Py samples, the SMR rapidly decreases with increasing Py thickness, eventually changing from positive to negative. In the case of intermediate Py thicknesses, the SMR consistently exhibits negative behavior. However, for thicker Py samples, the negative SMR values gradually decrease. This complex behavior is attributed to the dominant and competing mechanisms that contribute to SMR, including the spin Hall effect (or Rashba-induced effect) and its inverse effect, the orbital Hall effect and its inverse effect, as well as interfacial spin–orbit-coupling-induced spin-current-to-charge-current conversion. These findings would expand the arsenal for advanced spintronic applications based on 2D TMDs. [ABSTRACT FROM AUTHOR]

Real-time (RT) electronic structure methods provide a natural framework for describing light–matter interactions in arbitrary time-dependent electromagnetic fields (EMF). Optically induced excited state transitions are of particular interest, which require tuned EMF to drive population transfer to and from the specific state(s) of interest. Intersystem crossing, or spin-flip, may be driven through shaped EMF or laser pulses. These transitions can result in long-lived "spin-trapped" excited states, which are especially useful for materials requiring charge separation or protracted excited state lifetimes. Time-dependent configuration interaction (TDCI) is unique among RT methods in that it may be implemented in a basis of eigenstates, allowing for rapid propagation of the time-dependent Schrödinger equation. The recent spin–orbit TDCI (TD-SOCI) enables a real-time description of spin-flip dynamics in an arbitrary EMF and, therefore, provides an ideal framework for rational pulse design. The present study explores the mechanism of multiple spin-flip pathways for a model transition metal complex, FeCO, using shaped pulses designed to drive controlled intersystem crossing and charge transfer. These results show that extremely tunable excited state dynamics can be achieved by considering the dipole transition matrix elements between the states of interest. [ABSTRACT FROM AUTHOR]

Motivated by the booming development of spintronics based on chiral helical microstructures, we employed the standard nonequilibrium Green's function theory to study nonreciprocity and chirality of the heat generation and spin filtering in ferromagnetic helical chains. Our results demonstrate that magnetization, spin–orbit interaction, and nonstep electrostatic potential distribution by bias jointly determine nonreciprocity of the heat generation, and only spin–orbit interaction determines nonreciprocity of the spin-polarized current. Chirality of the heat generation and spin-polarized current is determined by both magnetization and spin–orbit interaction, and some quantitative relationships related to chirality were discovered. However, a transverse field can break these relations and suppress heat generation significantly and modulate nonreciprocity and chirality of the spin-polarized current effectively. By further simulating the critical electrostatic potential distribution, we found with the transverse field applied, compared to the case with zero temperature, that the finite temperature less than one characteristic phonon energy can suppress nonreciprocity of the heat generation while enhancing that of the spin filtering. In terms of chirality, compared to the left-handed helical structure, the right-handed one is more advantageous for designing spin filtering diodes. [ABSTRACT FROM AUTHOR]

We present a gauge-origin invariant exact two-component (X2C) approach within a modern density functional framework, supporting meta-generalized gradient approximations such as TPSS and range-separated hybrid functionals such as CAM-B3LYP. The complete exchange-correlation kernel is applied, including the direct contribution of the field-dependent basis functions and the reorthonormalization contribution from the perturbed overlap matrix. Additionally, the finite nucleus model is available for the electron-nucleus potential and the vector potential throughout. Efficiency is ensured by the diagonal local approximation to the unitary decoupling transformation in X2C as well as the (multipole-accelerated) resolution of the identity approximation for the Coulomb term (MARI-J, RI-J) and the seminumerical exchange approximation. Errors introduced by these approximations are assessed and found to be clearly negligible. The applicability of our implementation to large-scale calculations is demonstrated for a tin pincer-type system as well as low-valent tin and lead complexes. Here, the calculation of the Sn nuclear magnetic resonance shifts for the pincer-type ligand with about 2400 basis functions requires less than 1 h for hybrid density functionals. Further, the impact of spin–orbit coupling on the nucleus-independent chemical shifts and the corresponding ring currents of all-metal aromatic systems is studied. [ABSTRACT FROM AUTHOR]

In order to explore the interplay among heat, charge, and spin, we investigate the spin-related thermoelectricity of a hybrid double quantum dot Aharonov–Bohm interferometer with Rashba spin–orbit coupling (RSOC). Interestingly, the nonzero RSOC phase difference can induce significant spin-dependent thermoelectric transport. Not only can the strong violation of the Wiedemann-Franz law be obtained, but also a pure spin-Seebeck effect can be produced, which may serve as a pure spin-current generator. The influence of system parameters on thermoelectric coefficients (especially for spin counterparts) are analyzed in detail, and the underlying physics is further elucidated. Furthermore, the spin figure of merit can be much larger than the charge one, which, thus, provides a realistic possibility of engineering spin thermoelectric devices with high performance. These results obtained may be of interest for developing spin thermoelectric devices in the field of spin caloritronics. [ABSTRACT FROM AUTHOR]

This Tutorial article focuses on magnetic phenomena and material systems that have gained significant importance since the original development of mumax3, but are challenging to simulate for users who rely solely on the originally provided examples. Alongside the physical background, we provide hands-on examples of advanced magnetic systems, including detailed explanations of complete mumax3 input files (13 in total, often showing different ways to achieve things), and highlighting potential pitfalls where applicable. Specifically, we explore two approaches to incorporate spin–orbit torques in mumax simulations, considering the trade-off between versatility and speed. We also examine complex multilayer material stacks, including synthetic antiferromagnets, demonstrating different implementation methods that again vary in speed, versatility, and realism. A key criterion for selecting the optimal simulation strategy is its suitability for modeling systems where the magnetization varies significantly in the third dimension. The material covered in this Tutorial paper includes content developed for the mumax3 workshop presented during the summer of 2020 within the context of the IEEE online spintronics seminar, along with additional new topics. Throughout the explanations, we ensure broad applicability beyond specific examples. [ABSTRACT FROM AUTHOR]

Accurate description of electronic excited states of high-spin molecular species is a yet unsolved problem in modern electronic structure theory. A composite computational scheme developed in the present work contributes to solving this task for a challenging case of lanthanide-containing molecules. In the scheme, the highest-spin states whose wavefunctions are dominated by a single Slater determinant are described at the single-reference (SR) CCSD(T) level, whereas the lower-spin states, being inherently multiconfigurational in their nature, are treated with multireference (MR) methods, MRCI and/or CASPT2. An original technique which scales MR results against SR CCSD(T) ones to improve the accuracy in the former is proposed and examined, taking the example of 12 electronic states of gadolinium monoxide, X9Σ−, Y7Σ−, A′9Δ, A1′7Δ, A9Π, A17Π, B9Σ−, B17Σ−, C9Π, C17Π, D9Σ−, and D17Σ−, up to 35 000 cm−1. A multitude of the corresponding Ω (spin-coupled) states was then studied within the state-interacting approach employing the full Breit–Pauli spin–orbit coupling operator with CASSCF-generated ΛS states as a basis. For all ΛS and Ω states, the Gd–O bond lengths, spectroscopic constants ωe, ωexe, αe, and adiabatic excitation energies are obtained. The theoretical predictions are in good agreement with the experimental data, with deviations in excitation energies not exceeding 350 cm−1 (1 kcal/mol). The spectroscopic properties of the yet unobserved electronic states, A′9Δ, A1′7Δ, C9Π, C17Π, D9Σ−, and D17Σ−, are evaluated for the first time. [ABSTRACT FROM AUTHOR]

The transition of energy from the 4f to the 5d state is a fundamental element driving various applications, such as phosphors and optoelectronic devices. The positioning of the 4f ground states and the 5d excited states significantly influences this energy shift. In our research, we delve into the placement of these states utilizing a hybrid density functional theory (DFT) combined with spin–orbit coupling (SOC) via the supercell method. Additionally, we scrutinize the transition energy, applying the constrained density functional theory (cDFT) approach in conjunction with the ΔSCF method. Our study illustrates that the synergy of cDFT and SOC generates a discrepancy of about 2% for Ce1 and 4% for Ce2 when comparing the calculated results to experimental data. Moreover, We have determined the positions of the 4f ground states to be 2.73 eV above the Valence Band Maximum (VBM) for Ce1 and 2.70 eV for Ce2. We also note a tight correlation between the 5d levels identified in the experimental data and the theoretical outcomes derived from wave function calculations at the CASPT2 accuracy level. [ABSTRACT FROM AUTHOR]

The transition of energy from the 4f to the 5d state is a fundamental element driving various applications, such as phosphors and optoelectronic devices. The positioning of the 4f ground states and the 5d excited states significantly influences this energy shift. In our research, we delve into the placement of these states utilizing a hybrid density functional theory (DFT) combined with spin–orbit coupling (SOC) via the supercell method. Additionally, we scrutinize the transition energy, applying the constrained density functional theory (cDFT) approach in conjunction with the ΔSCF method. Our study illustrates that the synergy of cDFT and SOC generates a discrepancy of about 2% for Ce1 and 4% for Ce2 when comparing the calculated results to experimental data. Moreover, We have determined the positions of the 4f ground states to be 2.73 eV above the Valence Band Maximum (VBM) for Ce1 and 2.70 eV for Ce2. We also note a tight correlation between the 5d levels identified in the experimental data and the theoretical outcomes derived from wave function calculations at the CASPT2 accuracy level. [ABSTRACT FROM AUTHOR]