Spin-flip Mechanism Research Articles

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights.

Direct synthesis of thermodynamically less favorable (Z)-vinyl sulfones presents a notable challenge in organic synthesis. In addition, the development of a stereodivergent synthesis for (E)- and (Z)-vinyl sulfones is crucial but remains elusive. In this study, we present a hydrosulfonylation of aryl-substituted alkynes, achieving a stereodivergent synthesis of (E)- and (Z)-vinyl sulfones by leveraging both thermodynamic and kinetic controls. Notably, the synthesis of challenging (Z)-vinyl sulfones was achieved through a kinetically controlled process without the need for a catalyst. To synthesize (E)-vinyl sulfones, unconventional visible light-mediated isomerization was employed as a means of facilitating the transition to the thermodynamically favored form. The present study encompasses a comprehensive experimental and computational investigation, which provides valuable insights into the reaction mechanism. This investigation reveals two plausible isomerization pathways: a novel double spin-flip mechanism and a hydrogen atom transfer process in the presence of eosin Y. This study not only advances our understanding of isomerization mechanisms beyond conventional energy-transfer routes but also offers a robust and switchable strategy for synthesizing (E)- and (Z)-vinyl sulfones, thereby providing a versatile avenue for the creation of valuable compounds in the fields of organic synthesis and medicinal chemistry.

Understanding of complex spin up-conversion processes in charge-transfer-type organic molecules

Despite significant progress made over the past decade in thermally activated delayed fluorescence (TADF) molecules as a material paradigm for enhancing the performance of organic light-emitting diodes, the underlying spin-flip mechanism in these charge-transfer (CT)-type molecular systems remains an enigma, even since its initial report in 2012. While the initial and final electronic states involved in spin-flip between the lowest singlet and lowest triplet excited states are well understood, the exact dynamic processes and the role of intermediate high-lying triplet (T) states are still not fully comprehended. In this context, we propose a comprehensive model to describe the spin-flip processes applicable for a typical CT-type molecule, revealing the origin of the high-lying T state in a partial molecular framework in CT-type molecules. This work provides experimental and theoretical insights into the understanding of intersystem crossing for CT-type molecules, facilitating more precise control over spin-flip rates and thus advancing toward developing the next-generation platform for purely organic luminescent candidates.

Strain-Dependent Band Splitting and Spin-Flip Dynamics in Monolayer WS2

Triggered by the expanding demands of semiconductor devices, strain engineering of two-dimensional transition metal dichalcogenides (TMDs) has garnered considerable research interest. Through steady-state measurements, strain has been proved in terms of its modulation of electronic energy bands and optoelectronic properties in TMDs. However, the influence of strain on the spin-orbit coupling as well as its related valley excitonic dynamics remains elusive. Here, we demonstrate the effect of strain on the excitonic dynamics of monolayer WS2 via steady-state fluorescence and transient absorption spectroscopy. Combined with theoretical calculations, we found that tensile strain can reduce the spin-splitting value of the conduction band and lead to transitions between different exciton states via spin-flip mechanism. Our findings suggest that the spin-flip process is strain-dependent, provides a reference for application of valleytronic devices, where tensile strain is usually existing during their design and fabrication.

Itinerant magnetism, electronic properties and half-metallicity of Co2ZrSn and Co2HfSn Heusler alloys

Half-metallic ferromagnetic alloys are attracting considerable interest for their potential applications in spintronic devices. Co-based Heusler alloys are considered to be promising half-metallic compounds as they combine suitable magnetic, electronic and transport properties with compositional versatility and high thermal stability. In this work, Co 2 ZrSn and Co 2 HfSn Heusler alloys were studied by combining experimental and ab-initio investigations in order to accurately estimate their electronic density of states in proximity of the Fermi level and to determine their magnetic and electronic properties. Magnetization measurements, performed between 2 K and 550 K, suggest for both alloys a gradual transition from localized ferromagnetism to weak itinerant ferromagnetism with increasing temperature, well described by a simple mean field model up to the Curie temperature (454 K in Co 2 ZrSn and 432 K in Co 2 HfSn) and beyond. Ab-initio calculations were performed using two exchange-correlational functionals, PBE and PBE optimized for solids (PBEsol), in order to assess the reproducibility of theoretical results. Overall, band structures and density of states (DOS) diagrams indicated, for both compounds, the presence of a half-metallic band gap in the minority spin sub-band. The dependence of magnetic moments and band gap width on cell parameters is discussed in detail. Calculated magnetic moments and cell parameters satisfactorily match the experimental results obtained in this work and previously reported in the literature. • Itinerant weak ferromagnetic behaviour is confirmed for both alloys as they follow the Edwards-Wohlfarth model. • The mean field model indicates that the density of states profiles at the Fermi level are smooth. • Ab-initio calculation performed with PBE and PBEsol functionals show half-metallic behaviour at 0 K. • A crossover from localized magnetism to itinerant magnetism as function of temperature was found for both alloys. • The M/T crossover can be attributed to a change in spin-flip mechanism at low temperature.

Diffusion-Free Intramolecular Triplet–Triplet Annihilation in Engineered Conjugated Chromophores for Sensitized Photon Upconversion

The photon upconversion based on sensitized triplet–triplet annihilation (sTTA-UC) is a spin-flip mechanism exploited to recover the energy stored on dark triplet states in conjugated systems. In this process, a high-energy fluorescent singlet is created through the collision and fusion of two low-energy triplets belonging to different diffusing molecules. Its high yield in solution under low excitation intensity and noncoherent light highlighted the huge potential of sTTA-UC to provide a breakthrough in solar technologies. However, its diffusion-limited nature restrains its efficiency in the solid state. To overcome this issue, we propose a single-molecule system that is able to host simultaneously more than one triplet, thus enabling a diffusion-free intramolecular TTA. We obtain the first direct demonstration of intramolecular triplet fusion by tailored photoluminescence spectroscopy experiments, thus opening the way to realize a new family of single-molecule upconverters with huge potential in solar and lighting technologies by accessing the natural triplets’ energy reservoir.

Progress in ultrafast spintronics research

Ultrafast spintronics is one of the most promising fields for information processing technology innovation. When compared with traditional electronic devices, new spin-based devices have advantages such as low power consumption, high speed, and nonvolatility. Exploring novel physical phenomena and mechanisms relating to electronic spins significantly promotes the development of next-generation spintronic devices. In this review, we outline a sequence of advances in the fields of ultrafast magnetics and spintronics. First, a quick overview of spintronics and the discovery of ultrafast demagnetization induced by a femtosecond laser is provided. The proposed physical mechanisms and theories of ultrafast spin dynamics are then summarized, including the phenomenological three-temperature model, computations based on the time-dependent density functional theory, the Elliott-Yafet spin-flip mechanism, and the nonlocal superdiffusive spin transport model. Following that, the most recent experimental and theoretical studies on all-optical switching of ferrimagnetic and ferromagnetic metals are thoroughly reviewed. Furthermore, the discovery of hot-electron spin transport induced by ultrashort lasers as well as its influence on ultrafast magnetization dynamics, ultrafast spin transfer torque, spin injection into semiconductors, and spin accumulation and dissipation in hot-electron transport are described. The advancements in the optimization and manipulation of spintronics-based terahertz emitters are reviewed and analyzed. Finally, we discuss the current challenges in ultrafast spintronics research as well as possible future studies.

Equal-spin and oblique-spin crossed Andreev reflections in ferromagnet/Ising superconductor/ferromagnet junction

We study the subgap transport through a ferromagnet/Ising superconductor/ferromagnet (F/ISC/F) junction by solving the Bogoliubov--de Gennes equations. It is found that the crossed Andreev reflection (CAR) and local Andreev reflection (LAR) depend strongly on the spin-polarized F, the magnetization direction, and the Ising superconducting phase. For the same magnetization directions of the two F leads, the equal-spin CAR could take place due to the spin-flip mechanism induced by the Ising spin-orbit coupling and equal-spin-triplet pairing. Both equal-spin CAR and equal-spin LAR exhibit a remarkable magnetoanisotropy with period $\ensuremath{\pi}$ and show oscillatory behavior with a chemical potential. The equal-spin CAR is more prominent for half-metal F and double-band ISC while the normal CAR is completely suppressed. When the magnetization directions of the two F leads are different, the oblique-spin CAR occurs and its magnetoanisotropic period generally becomes $2\ensuremath{\pi}$ instead of $\ensuremath{\pi}$. In the oblique-spin CAR process, the spins of the electron and hole are neither parallel nor antiparallel. Furthermore, the property of oblique-spin CAR is very sensitive to the spin and valley degrees of freedom. The spin- and valley-polarized CAR can be achieved and controlled by the chemical potentials and the magnetization directions.

Phonon-assisted carrier tunneling with hyperfine-induced spin flip in coupled quantum dot systems

We calculate the rates of phonon-assisted hyperfine spin flips during electron and hole tunneling between quantum dots in a self-assembled quantum dot molecule. We show that the hyperfine process dominates over the spin-orbit-induced spin relaxation in magnetic fields up to a few Tesla for electrons, while for holes this cross-over takes place at field magnitudes of a fraction of Tesla, upon the assumption of a large $d$-shell admixture to the valence band state, resulting in a strong transverse hyperfine coupling. The interplay of the two spin-flip mechanisms leads to a minimum of the spin-flip probability, which is in principle experimentally measurable and can be used as a test for the presence of substantial transverse hyperfine couplings in the valence band.

Three States Involving Vibronic Resonance is a Key to Enhancing Reverse Intersystem Crossing Dynamics of an Organoboron-Based Ultrapure Blue Emitter

The recently developed narrow-band blue-emitting organoboron chromophores based on the multiple-resonance (MR) effect have now become one of the most important components for constructing efficient organic light emitting diodes (OLEDs). While they basically emit through fluorescence, they are also known for showing substantial thermally activated delayed fluorescence (TADF) even with a relatively large singlet–triplet gap (ΔEST). Indeed, understanding the reverse intersystem crossing (RISC) dynamics behind this peculiar TADF will allow judicious molecular designs toward achieving better performing OLEDs. Explaining the underlying nonadiabatic spin-flip mechanism, however, has often been equivocal, and how the sufficiently fast RISC takes place even with the sizable ΔEST and vanishingly small spin–orbit coupling is not well understood. Here, we show that a vibronic resonance, namely the frequency matching condition between the vibration and the electronic energy gap, orchestrates three electronic states together and this effect plays a major role in enhancing RISC in a typical organoboron emitter. Interestingly, the mediating upper electronic state is quite high in energy to an extent that its thermal population is vanishingly small. Through semiclassical quantum dynamics simulations, we further show that the geometry dependent non-Condon coupling to the upper triplet state that oscillates with the frequency ΔEST/ℏ is the main driving force behind the peculiar resonance enhancement. The existence of an array of vibrational modes with strong vibronic rate enhancements provides the ability to sustain efficient RISC over a range of ΔEST in defiance of the energy gap law, which can render the MR-emitters peculiar in comparison with more conventional donor–acceptor type emitters. Our investigation may provide a new guide for future blue emitting molecule developments.

Spin coherent manipulation in Josephson weak links

Novel designs of Josephson weak links based on semiconducting nanowires combined with circuit QED techniques have enabled the resolution of their fine structure due to spin-orbit interactions, opening a path towards Andreev spin qubits. Nevertheless, direct manipulation of the spin within a given Andreev state is in general suppressed compared to inter-doublet manipulation in the absence of Zeeman effects. In addition, noisy spin-flip mechanisms limit any coherent manipulation protocol to spin post-selection. We propose a combination of a spin polarization protocol analogous to sideband cooling with stimulated Raman adiabatic passage specifically tailored for these systems. We show this approach is robust for a large range of design parameters, including the currently rather stringent coherence times.

Electrically controlled emission from singlet and triplet exciton species in atomically thin light-emitting diodes

Excitons are composite bosons that can feature spin singlet and triplet states. In usual semiconductors, without an additional spin-flip mechanism, triplet excitons are extremely inefficient optical emitters. Transition metal dichalcogenides (TMDs), with their large spin-orbit coupling, have been of special interest for valleytronic applications for their coupling of circularly polarized light to excitons with selective valley and spin$^{1-4}$. In atomically thin MoSe$_2$/WSe$_2$ TMD van der Waals (vdW) heterostructures, the unique atomic registry of vdW layers provides a quasi-angular momentum to interlayer excitons$^{5,6}$, enabling emission from otherwise dark spin triplet excitons. Here, we report electrically tunable spin singlet and triplet exciton emission from atomically aligned TMD heterostructures. We confirm the spin configurations of the light-emitting excitons employing magnetic fields to measure effective exciton g-factors. The interlayer tunneling current across the TMD vdW heterostructure enables the electrical generation of singlet and triplet exciton emission in this atomically thin PN junction. We demonstrate electrically tunability between the singlet and triplet excitons that are generated by charge injection. Atomically thin TMD heterostructure light emitting diodes thus enables a route for optoelectronic devices that can configure spin and valley quantum states independently by controlling the atomic stacking registry.

Transient circular dichroism and exciton spin dynamics in all-inorganic halide perovskites

All-inorganic metal halides perovskites (CsPbX3, X = Br or Cl) show strong excitonic and spin-orbital coupling effects, underpinning spin-selective excitonic transitions and therefore exhibiting great promise for spintronics and quantum-optics applications. Here we report spin-dependent optical nonlinearities in CsPbX3 single crystals by using ultrafast pump-probe spectroscopy. Many-body interactions between spin-polarized excitons act like a pseudo-magnetic field and thus lift the degeneracy of spin states resulting in a photoinduced circular dichroism. Such spontaneous spin splitting between “spin-up” and “spin-down” excitons can be several tens of milli-electron volts under intense excitations. The exciton spin relaxation time is ~20 picoseconds at very low pump fluence, the longest reported in the metal halides perovskites family at room temperature. The dominant spin-flip mechanism is attributed to the electron-hole exchange interactions. Our results provide essential understandings towards realizing practical spintronics applications of perovskite semiconductors.

Spin–flip manipulation in HgTe/CdTe heterostructure interface states with Rashba and Dresselhuas spin–orbit interactions

We investigate theoretically the electron transport through (001) HgTe/CdTe quantum well heterostructures with inverted-band in planar geometry, where Dirac-like spin–momentum locked interface states have been predicted to be formed and topologically protected against perturbations preserving time-reversal symmetry. In this work, k.p theory and scattering matrix method are used to characterize the interface states of the (001) HgTe/CdTe heterostructure as well as to understand the influence of external electric fields. We find distinct features of the transmission and conductance by considering both Rashba and Dresselhuas spin–orbit interactions. The efficient spin–flip conversion between spin-up and spin-down channels are found by tuning the strength of Rashba and Dresselhuas spin–orbit interactions. It is shown that ideal spin–flip efficiency, i.e., the complete spin–flip, can be achieved with specific spin–orbit coupling strengths. This spin–flip mechanism provides us a realistic way to manipulate the spin orientation which can be constructed low-power information processing device. Furthermore, we address the topological edge states induced unique spin manipulation capability by comparing with the conventional electron transport properties in bulk states. In addition, we analyze the transport behavior when the system in the presence of Zeeman term which may play an important role for a high magnetic field in a realistic experimental setup.

Spin-flip relaxation mechanism in self-assembled quantum dots via phonon emission

The spin-flip relaxation time for electrons in self-assembled coupled quantum dots (SACQDs) due to emission of acoustic phonons is presented. We focus on arbitrary shaped quantum dots made with InAs embedded in a wetting layer InAs and surrounded by GaAs. The electron states are calculated using the 8-band strain dependent theory. The deformation potential and the piezo- electric acoustic phonon modes are employed to estimate the electron-phonon coupling. Spin-flip time is calculated by Fermi’s Golden Rule and its dependence on the shape of the QDs, the size and the lattice temperature is investigated.

Spin-orbit Interactions for Singlet-Triplet Qubits in Silicon.

Spin-orbit coupling is relatively weak for electrons in bulk silicon, but enhanced interactions are reported in nanostructures such as the quantum dots used for spin qubits. These interactions have been attributed to various dissimilar interface effects, including disorder or broken crystal symmetries. In this Letter, we use a double-quantum-dot qubit to probe these interactions by comparing the spins of separated singlet-triplet electron pairs. We observe both intravalley and intervalley mechanisms, each dominant for [110] and [100] magnetic field orientations, respectively, that are consistent with a broken crystal symmetry model. We also observe a third spin-flip mechanism caused by tunneling between the quantum dots. This improved understanding is important for qubit uniformity, spin control and decoherence, and two-qubit gates.

Origins of overshoots in the exciton spin dynamics in semiconductors

We investigate the origin of overshoots in the exciton spin dynamics after resonant optical excitation. As a material system, we focus on diluted magnetic semiconductor quantum wells as they provide a strong spin-flip scattering for the carriers. Our study shows that overshoots can appear as a consequence of radiative decay even on the single-particle level in a theory without any memory. The magnitude of the overshoots in this case depends strongly on the temperature as well as the doping fraction of the material. If many-body effects beyond the single-particle level become important so that a quantum-kinetic description is required, a spin overshoot appears already without radiative decay and is much more robust against variations of system parameters. We show that the origin of the spin overshoot can be determined either via its temperature dependence or via its behavior for different doping fractions. The results can be expected to apply to a wide range of semiconductors as long as radiative decay and a spin-flip mechanism are present.

Point-Like Rashba Interactions as Singular Self-Adjoint Extensions of the Schrödinger Operator in One Dimension

We consider singular self-adjoint extensions for the Schr\{o}dinger operator of spin-$1/2$ particle in one dimension. The corresponding boundary conditions at a singular point are obtained. There are boundary conditions with the spin-flip mechanism, i.e. for these point-like interactions the spin operator does not commute with the Hamiltonian. One of these extensions is the analog of zero-range $\delta$-potential. The other one is the analog of so called $\delta^{(1)}$-interaction. We show that in physical terms such contact interactions can be identified as the point-like analogues of Rashba Hamiltonian (spin-momentum coupling) due to material heterogeneity of different types. The dependence of the transmissivity of some simple devices on the strength of the Rashba coupling parameter is discussed. Additionally, we show how these boundary conditions can be obtained in the non-relativistic limit of Dirac Hamiltonian.

Spin qubits: spin relaxation in coupled quantum dots

The spin-flip scattering mechanism in coupled self-assembled quantum dots made with InAs/GaAs with the use of realistic material parameters is theoretically and numerically investigated. The electron wave functions within the coupled system have been calculated by the 8-band strain dependent theory. The phonon coupling to electrons is described by deformation potential and piezoelectric acoustic phonons. First order perturbation theory has been employed to evaluate the spin relaxation rates and spin-flip time T1. The numerical results show that parameters like the interdot distance and the applied static magnetic field are of crucial importance in spin-flip mechanism. The spin relaxation time has been also studied by varying the lattice temperature and by showing the differences between the quantum computing operation temperature ( K) and large temperatures.

Mn–O–O Electron Spin Flip Mechanism Triggered by the Visible-Light Irradiation for the Generation of an Active Mn(V)–Oxo Complex from O2: Insight from Density Functional Calculations

We reveal a new activation mechanism of O2 by electron spin flip for the formation of a high-valent Mn(V)–oxo corrolazine complex under O2 atmosphere and visible-light irradiation conditions. Ab initio calculations show that a loosely associated triplet complex from a quintet manganese corrolazine with a triplet O2 is formed initially in reaction. The subsequent strong bonding interactions between dioxygen with the manganese corrolazine, triggered by the visible-light irradiation, give rise to an increase in orbital splitting energy and drive the spin flip of electrons located at Mn and their rearrangement among the frontier orbitals, yielding the radical-like [Mn]–O–O species with high reactivity, which can easily abstract the hydrogen of the substrate to form the high-valent Mn(V)–oxo active oxidant through the following rebound reaction. Here the coupling interactions of dxz and dyz of Mn with the corresponding πxz23 and πyz23 orbitals of O2 may form two new extending π bonds, πxz34 and πyz34. Such an ...

Electron–electron interactions of the multi-Cooper-pairs in the 1D limit and their role in the formation of global phase coherence in quasi-one-dimensional superconducting nanowire arrays

Nanostructuring of superconducting materials to form dense arrays of thin parallel nanowires with significantly large transverse Josephson coupling has proven to be an effective way to increase the upper critical field of superconducting elements by as much as two orders of magnitude as compared to the corresponding bulk materials and, in addition, may cause considerable enhancements in their critical temperatures. Such materials have been realized in the linear pores of mesoporous substrates or exist intrinsically in the form of various quasi-1D crystalline materials. The transverse coupling between the superconducting nanowires is determined by the size-dependent coherence length ξ0. In order to obtain ξ0 over the Langer–Ambegaokar–McCumber–Halperin (LAMH) theory, extensive experimental fitting parameters have been required over the last 40 years. We propose a novel Monte Carlo algorithm for determining ξ0 of the multi-Cooper pair system in the 1D limit. The concepts of uncertainty principle, Pauli-limit, spin flip mechanism, electrostatic interaction, thermal perturbation and co-rotating of electrons are considered in the model. We use Pb nanowires as an example to monitor the size effect of ξ0 as a result of the modified electron-electron interaction without the need for experimental fitting parameters. We investigate how the coherence length determines the transverse coupling of nanowires in dense arrays. This determines whether or not a global phase-coherent state with zero resistance can be formed in such arrays. Our Monte Carlo results are in very good agreement with experimental data from various types of superconducting nanowire arrays.