Spin Relaxation Processes Research Articles

Toward Quantum Noses: Quantum Chemosensing Based on Molecular Qubits in Metal-Organic Frameworks.

ConspectusQuantum sensing leverages quantum properties to enhance the sensitivity and resolution of sensors beyond their classical sensing limits. Quantum sensors, such as diamond defect centers, have been developed to detect various physical properties, including magnetic fields and temperature. However, the spins of defects are buried within dense solids, making it difficult for them to strongly interact with molecular analytes. Therefore, nanoporous materials have been implemented in combination with electron spin center of molecules (molecular qubits) to produce quantum chemosensors that can distinguish various chemical substances. Molecular qubits have a uniform structure, and their properties can be precisely controlled by changing their chemical structure. Metal-organic frameworks (MOFs) are suitable for supporting molecular qubits because of their high porosity, structural regularity, and designability. Molecular qubits can be inserted in the MOF structures or adsorbed as guest molecules. The qubits in the MOF can interact with analytes upon exposure, providing an effective and tunable sensing platform.In this Account, we review the recent progress in qubit-MOF hybrids toward the realization of room-temperature quantum chemosensing. Molecular qubits can be introduced in controlled concentrations at targeted positions by exploiting metal ions, ligands, or guests that compose the MOF. Heavy metal-free organic chromophores have several outstanding features as molecular qubits; namely, they can be initialized by light irradiation and exhibit relatively long coherence times of submicroseconds to microseconds, even at room temperature. One detection method involves monitoring the hyperfine interaction between the electron spins of the molecular qubits and the nuclear spins of the analyte incorporated in the pore. There is also an indirect detection method that relies on the motional change in molecular qubits. If the motion of the molecular qubit changes with the adsorption of the analyte, it can be detected as a change in the spin relaxation process. This mechanism is unique to qubits exposed in nanopores, not observed in conventional qubits embedded in dense solids.By maximizing the guest recognition ability of MOFs and the environmental sensitivity of qubits, quantum chemosensing that recognizes specific chemical species in a highly selective and sensitive manner may be possible. It is difficult to distinguish between diverse chemical species by employing only one combination of MOF and qubit, but by creating arrays of different qubit-MOF hybrids, it would become possible to distinguish between various analytes based on pattern recognition. Inspired by the human olfactory mechanism, we propose the use of multiple qubit-MOF hybrids and pattern recognition to identify specific molecules. This system represents a quantum version of olfaction, and thus we propose the concept of a "quantum nose." Quantum noses may be used to recognize biometabolites and biomarkers and enable new medical diagnostic technologies and olfactory digitization.

(Keynote) Experimental and Computational Insights into Electronic Structure and Redox Properties of Bare and Doped Co3O4 Nanocrystals of Euhedral Morphology and Their Heterojunctions with Alien Oxides and Carbon Materials

One of the most attractive oxide materials with remarkable record of widespread applications are cobalt spinels and their derivatives obtained by doping with alien redox (3dn) and nonredox (Li) cations or via hybridization with other oxides (CeO2, TiO2, a-Al2O3) or carbon support. They have recently received a great deal of theoretical and practical attention because of an outstanding activity in many redox processes important for photo/electro/catalysis. Among many potential applications, their relevance as promising substitutes for platinum in oxygen reduction reaction (ORR) or oxygen evolution reaction (OER) can be mentioned, in particular. The properties of nanostructured cobalt spinel materials depend on their size, shape, doping and interfacing features. In this context, euhedral spinel nanocrystals that expose well defined crystallographic planes, allow for sensible investigations into establishment of the surface/bulk structure-redox reactivity relationships in real conditions.In this presentation application of S/TEM and inverse Wulff hull matching techniques supported by image simulation was discussed for elucidation the mechanism of hydrothermal synthesis of euhedral cobalt spinel nanocrystals the their shape retrieving. Periodic spin unrestricted DFT-PW91+U and hybrid DFT/HSE06 calculations were applied for modeling the morphology, structure and electronic properties (DOS structure) relevant for redox behavior of bare and doped cobalt spinel nanocrystals. The results allowed for thorough characterization of the structure and reconstruction of the exposed low index (100), (110), and (111) planes, and explain the influence of dopants. The effect of the valence state of lithium (Li+ or Li0), and its locus on the valence pining of the cobalt cations was determined. DFT calculations together with the ab initio thermodynamic modeling were used to study the electronic structure of the created defects, and stability of different terminations of cobalt spinel and Li-doped Co3O4 under various redox conditions. The associated electronic and spin relaxation processes were discussed as well. For the most stable stoichiometric (100) and (111) facets, the surface redox state diagrams in a wide stoichiometry range were constructed, and analyzed in detail. Intrinsic charge transfer processes involving electron (n-conductivity) and hole (p-conductivity) transfer between the octahedral and tetrahedral cobalt cations were modeled using a small polaron approximation (Marcus-Dupuis model). Formation of n-p junctions (Co3O4|CeO2, Li-Co3O4|CeO2) and MxCo3-xO4/carbon hybrids were analyzed by S/TEM, XPS spectroscopy (band alignment), contactless electronic conductivity and work function measurements, corroborated by DFT modeling. The redox properties of the interface and spinel faceting, and the role of electric conductivity and the nature of the carbon support functional groups were discussed in the context of the ORR, OER performance, and catalytic redox reactivity (activation of O2).AcknowledgmentsS.W. thanks for the financial support of the project “High-performance electrocatalyst for oxygen reduction reaction with low platinum content” carried on within the Program “Pearls of Science” of the Ministry of Education and Science of Poland.

Rashba Effect and Spin-Dependent Excitonic Properties in Chiral Two-Dimensional/Three-Dimensional Composite Perovskite Films.

Among various chiral semiconductor materials, chiral two-dimensional (2D)/three-dimensional (3D) composite perovskites (CPs) offer the benefits of strong interface asymmetry and energy transfer between 2D and 3D phases, making the chiral CPs promising for spintronic devices. Therefore, understanding their spintronic properties will be greatly important for expanding their relevant applications. In this work, we synthesized one pair of chiral 2D/3D CP films. Their Rashba effect and spin relaxation process have been investigated by polarization-dependent femtosecond transient absorption spectroscopy. Interestingly, under left- and right-handed circularly polarized light (CPL) excitation, a two-photon emission intensity difference is observed in chiral 2D/3D CP films at 298 K. This work sheds light on the spin-dependent excitonic characteristics of chiral 2D/3D CPs and confirms the feasibility of their application in near-infrared CPL detection.

Spin relaxation time enhancement induced by polarization field screening in an InGaN/GaN quantum well

A correlation between the spin-polarized carrier transfer and spin relaxation processes of a two-dimensional electron gas (2DEG) in an InGaN/GaN quantum well (QW) is investigated by time-resolved Kerr rotation spectroscopy at low temperature. Upon resonant excitation with the GaN barrier band edge energy, the spin polarization of the 2DEG in the QW is acquired from the transfer of spin-polarized photoexcited carriers. Significantly, the spin relaxation time of the 2DEG is enhanced to be as long as 1 ns along with the carrier transfer. It is demonstrated that by tailoring the Rashba and Dresselhaus spin–orbit couplings to approach a spin-degenerate surface, the screening effect of the polarization field leads to a longer spin relaxation time and effective manipulation of the spin relaxation. The polarization field screening induced enhancement of the spin relaxation time is significant in the way for the development of GaN-based spintronic devices.

Spin Coherence and Spin Relaxation in Hybrid Organic-Inorganic Lead and Mixed Lead-Tin Perovskites.

Metal halide perovskites make up a promising class of materials for semiconductor spintronics. Here we report a systematic investigation of coherent spin precession, spin dephasing and spin relaxation of electrons and holes in two hybrid organic-inorganic perovskites MA0.3FA0.7PbI3 and MA0.3FA0.7Pb0.5Sn0.5I3 using time-resolved Faraday rotation spectroscopy. With applied in-plane magnetic fields, we observe robust Larmor spin precession of electrons and holes that persists for hundreds of picoseconds. The spin dephasing and relaxation processes are likely to be sensitive to the defect levels. Temperature-dependent measurements give further insights into the spin relaxation channels. The extracted electron Landé g-factors (3.75 and 4.36) are the biggest among the reported values in inorganic or hybrid perovskites. Both the electron and hole g-factors shift dramatically with temperature, which we propose to originate from thermal lattice vibration effects on the band structure. These results lay the foundation for further design and use of lead- and tin-based perovskites for spintronic applications.

Electron spin resonance and induction heating studies of zinc substituted (Mn, Co) ferrite nanoparticles for potential magnetic hyperthermia applications

This study presents an investigation on the various spin relaxation processes taking place at X-Band microwave energy in Zn substituted MnFe2O4 and CoFe2O4 and their induction heating studies. The material properties of these citric acid assisted sol-gel synthesized nanoparticles have been explored using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscope, Vibrating sample magnetometer (VSM) and Electron spin resonance spectroscopy. XRD and Rietveld refinement confirm the face centered cubic spinel structure of the synthesized samples, which is further supported by the observation of absorption bands characteristic of the spinel ferrites in the FTIR spectra. The remanence, coercivity and effective magnetocrystalline anisotropy values from VSM studies show lower value with zinc substitution which is desirable for biomedical application. Various spin resonance parameters like gyromagnetic ratio, peak to peak linewidth, resonance field, spin-lattice and spin-spin relaxation times have been calculated. The induction heating studies of the samples in an alternating magnetic field have been carried out using a field strength of 4.58 × 109 Am-1s-1. All the investigated MNPs are able to raise the temperature to the therapeutic limit of 42–45 °C. The specific absorption rate (SAR) which describe the heating potential of the MNPs is calculated using four different concentrations of each sample - 5 mg mL-1, 10 mg mL-1, 15 mg mL-1 and 20 mg mL-1. SAR values are found to decrease with increase in concentration and achieve the highest value of 303 W/g for Co0.5Zn0.5Fe2O4 nanoparticles with 5 mg mL-1 concentration. The ability of the MNPs to give rise to the therapeutic temperature points toward their suitability as an effective heat mediator in magnetic hyperthermia treatment of cancer.

Low-frequency spin dynamics in diluted magnetic semiconductors

The low-frequency dynamical magnetic properties in paramagnetic diluted magnetic semiconductors are addressed in the framework of the dynamical mean-field theory applied for the Kondo lattice model. In the infinite-dimensional limit, a set of self-consistent equations is derived so the single-particle Green's function and its self-energy can be evaluated numerically. In terms of the Green's function and self-energies, the local dynamical spin susceptibility function and then the spin-relaxation rate are explicitly expressed based on the Baym-Kadanoff approach. It is found that the spin fluctuations become dominated, indicated by the sharp peak appearing at the low frequency of the spin dynamical susceptibility function in the case of large magnetic coupling and temperature close to the paramagnetic-ferromagnetic transition point. The low-frequency spin dynamic in the systems is also addressed in the signatures of the spin-relaxation process. In the case of large temperature and small magnetic coupling, the spin-relaxation rate releases the scenario of the Korringa process specifying the weak correlation systems likely normal metals. Otherwise, i.e., at small temperature and large magnetic coupling, we find exponential behavior of the spin-relaxation rate versus temperature. Moreover, at a temperature approaching the paramagnetic-ferromagnetic transition point, one finds sharp suppression of the spin-relaxation rate or speeding up of the spin-relaxation time. These scenarios are attributed to the appearance of the magnetic coherence bound state or the spin clusters in diluted magnetic semiconductors due to the strongly magnetic correlations.

Strong variation of spin-orbit torques with relative spin relaxation rates in ferrimagnets

Spin-orbit torques (SOTs) have been widely understood as an interfacial transfer of spin that is independent of the bulk properties of the magnetic layer. Here, we report that SOTs acting on ferrimagnetic FexTb1-x layers decrease and vanish upon approaching the magnetic compensation point because the rate of spin transfer to the magnetization becomes much slower than the rate of spin relaxation into the crystal lattice due to spin-orbit scattering. These results indicate that the relative rates of competing spin relaxation processes within magnetic layers play a critical role in determining the strength of SOTs, which provides a unified understanding for the diverse and even seemingly puzzling SOT phenomena in ferromagnetic and compensated systems. Our work indicates that spin-orbit scattering within the magnet should be minimized for efficient SOT devices. We also find that the interfacial spin-mixing conductance of interfaces of ferrimagnetic alloys (such as FexTb1-x) is as large as that of 3d ferromagnets and insensitive to the degree of magnetic compensation.

Front Cover: Static and Dynamic Magnetic Properties of a Co(II)‐Complex with N2O2 Donor Set – A Theoretical and Experimental Study (Eur. J. Inorg. Chem. 10/2023)

The Front Cover shows a Co(II) ion that is actually chelated by two monoanionic sulfur-containing Schiff base ligands. Each ligand contributes with a nitrogen and an oxygen atom to form the illustrated pseudo-tetrahedral coordination. A magnetic field prevents spin transversal by quantum tunnelling at very low temperature, since the spin transversal is connected to a Zeeman energy difference that needs to be compensated by energy from quantized atomic movements. At higher temperatures, the local anisotropy due to the strong orbital momentum mixing to the spin 3/2 of the Co(II) plays a more crucial role, and two-phonon spin-relaxation processes become more and more dominant. More information can be found in the Research Article by B. Schwarz, K. C. Mondal and co-workers.

Dopant-Induced Slow Spin Relaxation in CsPbBr3 Perovskite Nanocrystals

Lead halide perovskites comprise a class of materials holding great promise for spin-related applications due to their strong spin–orbital coupling (SOC) effect. However, the strong SOC also shortens the lifetime of spin states and thus limits their further application. Herein we take Bi-doped CsPbBr3 perovskite nanocrystals (NCs) as an example material to study how metal doping can affect the spin-relaxation process, by using circularly polarized transient absorption (TA) spectroscopy. We demonstrate that in undoped CsPbBr3 NCs the spin relaxation is governed by the electron–hole exchange (EHE) mechanism and in doped NCs the Bi-dopants significantly slow down the spin relaxation by creating an ultrafast (∼0.13 ps) hole trapping process and thus disturbing the EHE spin de-coherent process. By tuning the Bi-doping ratio, the spin-relaxation time in doped NCs is prolonged to ∼24.6 ps, much longer than that (∼4.4 ps) in undoped NCs. Our finding suggests that doping a metal element is an effective way to tune the spin relaxation in perovskites NCs and likely also in many other types of quantum-confined NCs.

Ratiometric Raman and Luminescent Thermometers Constructed from Dysprosium Thiocyanidometallate Molecular Magnets

AbstractMolecular crystals acting as temperature sensors, designed for multiple measurement techniques, can be a promising pathway for self‐calibrating thermometers. The molecular assemblies [DyxIIIY1–xIII(phen)2(μ‐OH)2(H2O)2]·[AuI(SCN)2]2·phen·0.5MeCN·0.5H2O (x = 0, 0.1, 0.02; phen = 1,10‐phenanthroline) which contain weakly bonded lanthanide(III) and Au(I) metal complexes are reported. They have Raman scattering in the low‐frequency (LF) region with sharp peaks, one of the prerequisites to design Raman thermometers. The Raman thermometric behaviors are characterized by three vibrational bands, and their thermal sensitivity is compared with their emission thermometric ability. The LF phonon linked with the Au···Au vibration helps increase the thermometric sensitivity of emission and Raman thermometers. Additionally, magnetically diluted complexes containing both Dy3+ and Y3+ ions are prepared to demonstrate the effect of temperature sensing capability through Raman and emission spectroscopy among isostructural mixed‐metal materials. Compounds are immersed inside various benchtop solvents to unravel the robustness and functioning of Raman thermometers. Furthermore, they reveal single‐molecule magnet properties, which disclose the effect of LF phonons on the spin relaxation process. Therefore, the reported molecular materials are Raman and luminescent thermometers, and they contain a molecular magnetic center with thiocyanidoaurate ions playing a critical role due to their emissive and Raman activities.

Spin relaxation in copper channels with submicron cross sections

We review our recent experimental studies of the spin relaxation processes in the submicron copper channels of nonlocal spin valves (NLSV). Long spin relaxation lengths up to 3.0 μm at low temperatures are demonstrated in highly conductive copper channels with residual resistivity ratios up to 6. An unexpected anisotropy of spin relaxation is observed and can be attributed to the surface spin–orbit effects. An unusual scaling of the Kondo spin relaxation is established experimentally and can be explained by overlapping Kondo screening clouds. Our results demonstrate the technological potential of copper as a spin transport channel in spintronics and highlights unanswered fundamental questions related to the spin relaxation processes.

Observation of an anisotropic ultrafast spin relaxation process in large-area WTe2 films

Weyl semimetal Td-WTe2 hosts the natural broken inversion symmetry and strong spin–orbit coupling, which contains profound spin-related physics within a picosecond timescale. However, the comprehensive understanding of ultrafast spin behaviors in WTe2 is lacking due to its limited quality of large-scale films. Here, we report on an anisotropic ultrafast spin dynamics in highly oriented Td-WTe2 films using a femtosecond pump–probe technique at room temperature. A transient spin polarization-flip transition as fast as 0.8 ps is observed upon photoexcitation. The inversed spin is subsequently scattered by defects with a duration of about 5.9 ps. The whole relaxation process exhibits an intriguing dual anisotropy of sixfold and twofold symmetries, which stems from the energy band anisotropy of the WTe2 crystalline structure and the matrix element effect, respectively. Our work enriches the insights into the ultrafast opto-spintronics in topological Weyl semimetals.

Motional clustering in supra-[formula omitted] conformational exchange influences NOE cross-relaxation rate

Biomolecular spin relaxation processes, such as the NOE, are commonly modeled by rotational τc-tumbling combined with fast motions on the sub-τc timescale. Motions on the supra-τc timescale, in contrast, are considered to be completely decorrelated to the molecular tumbling and therefore invisible. Here, we show how supra-τc dynamics can nonetheless influence the NOE build-up between methyl groups. This effect arises because supra-τc motions can cluster the fast-motion ensembles into discrete states, affecting distance averaging as well as the fast-motion order parameter and hence the cross-relaxation rate. We present a computational approach to estimate methyl–methyl cross-relaxation rates from extensive (>100×τc) all-atom molecular dynamics (MD) trajectories on the example of the 723-residue protein Malate Synthase G. The approach uses Markov state models (MSMs) to resolve transitions between metastable states and thus to discriminate between sub-τc and supra-τc conformational exchange. We find that supra-τc exchange typically increases NOESY cross-peak intensities. The methods described in this work extend the theory of modeling sub-μs dynamics in spin relaxation and thus contribute to a quantitative estimation of NOE cross-relaxation rates from MD simulations, eventually leading to increased precision in structural and functional studies of large proteins.

Dipolar spin relaxation of divacancy qubits in silicon carbide

Divacancy spins implement qubits with outstanding characteristics and capabilities in an industrial semiconductor host. On the other hand, there are still numerous open questions about the physics of these important defects, for instance, spin relaxation has not been thoroughly studied yet. Here, we carry out a theoretical study on environmental spin-induced spin relaxation processes of divacancy qubits in the 4H polytype of silicon carbide (4H-SiC). We reveal all the relevant magnetic field values where the longitudinal spin relaxation time T1 drops resonantly due to the coupling to either nuclear spins or electron spins. We quantitatively analyze the dependence of the T1 time on the concentration of point defect spins and the applied magnetic field and provide an analytical expression. We demonstrate that dipolar spin relaxation plays a significant role both in as-grown and ion-implanted samples and it often limits the coherence time of divacancy qubits in 4H-SiC.

Ab initio ultrafast spin dynamics in solids

Spin relaxation and decoherence is at the heart of spintronics and spin-based quantum information science. Currently, theoretical approaches that can accurately predict spin relaxation of general solids including necessary scattering pathways and capable for ns to ms simulation time are urgently needed. We present a first-principles real-time density-matrix approach based on Lindblad dynamics to simulate ultrafast spin dynamics for general solid-state systems. Through the complete first-principles descriptions of pump, probe and scattering processes including electron-phonon, electron-impurity and electron-electron scatterings with self-consistent electronic spin-orbit couplings, our method can directly simulate the ultrafast pump-probe measurements for coupled spin and electron dynamics over ns at any temperatures and doping levels. We first apply this method to a prototypical system GaAs and obtain excellent agreement with experiments. We find that the relative contributions of different scattering mechanisms and phonon modes differ considerably between spin and carrier relaxation processes. In sharp contrast to previous work based on model Hamiltonians, we point out that the electron-electron scattering is negligible at room temperature but becomes dominant at low temperatures for spin relaxation in n-type GaAs. We further examine ultrafast dynamics in novel spin-valleytronic materials - monolayer and bilayer WSe2 with realistic defects. We find that spin relaxation is highly sensitive to local symmetry and chemical bonds around defects. Our work provides a predictive computational platform for spin dynamics in solids, which has unprecedented potentials for designing new materials ideal for spintronics and quantum information technology.

Sub-100 femtosecond time scale spin dynamics in epitaxial Fe3O4 thin film

We have investigated the ultrafast laser-induced magnetization and reflectivity dynamics in the Fe3O4 thin film using all-optical pump–probe measurements. The high-quality of our sample is verified by the temperature-dependent static magnetic properties, showing a clear Verwey transition. Although the Fe3O4 is predicted to be a half-metal, the demagnetization process upon laser incident shows a transition-metal-like behavior. The demagnetization characteristic time has been found to be in sub-100 fs (fs) time scale, suggesting the dominant interaction of hole spin-flip processes. The spin relaxation process has been found to be around 600 fs, which is attributed to the electron–phonon coupling in accordance to the observed two electron–phonon coupling modes in reflectivity dynamics. Our results provide new insight into the ultrafast laser-induced spin dynamics in half-metallic ferrimagnet.

Hyperfine-Induced Electron-Spin Dephasing in Negatively Charged Colloidal Quantum Dots: A Survey of Size Dependence.

The electron spin relaxation processes are complicated in semiconductor quantum dots. Different spin relaxation mechanisms may result in an increased or decreased spin relaxation rate with the size. The information on size-dependent spin dynamics helps to clarify and better understand the underlying spin relaxation processes. We investigate the size dependence of the electron spin dynamics in negatively photocharged CdSe and CdS colloidal quantum dots by time-resolved ellipticity spectroscopy. It is revealed that the electron spin dephasings of photodoped electron in zero or weak magnetic fields are dominated by the electron-nuclear hyperfine interaction for all measured samples. The hyperfine-induced electron spin dephasing time is ∼1-2 ns at room temperature and decreases with decreasing the size D. In addition to a size-dependent dephasing time that is directly proportional to D3/2, our measurements also show a size-independent time component, likely due to the laser-induced nuclear spin ordering.

Magnetic torque enhanced by tunable dipolar interactions

We use tunable dipolar-interactions between the spins of nitrogen-vacancy (NV) centers in diamond to rotate a diamond crystal. Specifically, we employ cross-relaxation between the electronic spin of pairs of NV centers in a trapped diamond to enhance the anisotropic NV paramagnetism and thus to increase the associated spin torque. Our observations open a path towards the use of mechanical oscillators to detect paramagnetic defects that lack optical transitions, to investigation of angular momentum conservation in spin relaxation processes and to novel means of cooling the motion of mechanical oscillators.

Relaxation of a dense ensemble of spins in diamond under a continuous microwave driving field

Decoherence of Rabi oscillation in a two-level quantum system consists of two components, a simple exponential decay and a damped oscillation. In dense-ensemble spin systems like negatively charged nitrogen-vacancy (NV−) centers in diamond, fast quantum state decoherence often obscures clear observation of the Rabi nutation. On the other hand, the simple exponential decay (or baseline decay) of the oscillation in such spin systems can be readily detected but has not been thoroughly explored in the past. This study investigates in depth the baseline decay of dense spin ensembles in diamond under continuously driving microwave (MW). It is found that the baseline decay times of NV− spins decrease with the increasing MW field strength and the MW detuning dependence of the decay times shows a Lorentzian-like spectrum. The experimental findings are in good agreement with simulations based on the Bloch formalism for a simple two-level system in the low MW power region after taking into account the effect of inhomogeneous broadening. This combined investigation provides new insight into fundamental spin relaxation processes under continuous driving electromagnetic fields and paves ways to better understanding of this underexplored phenomena using single NV− centers, which have shown promising applications in quantum computing and quantum metrology.