Showing papers on "Spin states published in 2021"

Electronic Spin Moment As a Catalytic Descriptor for Fe Single-Atom Catalysts Supported on C2N.

Abstract: The electrocatalytic activity of transition-metal-based compounds is strongly related to the spin states. However, the underlying relationship connecting spin to catalytic activity remains unclear. Herein, we carried out density functional theory calculations on oxygen reduction reaction (ORR) catalyzed by Fe single-atom supported on C2N (C2N-Fe) to shed light on this relationship. It is found that the change of electronic spin moments of Fe and O2 due to molecular-catalyst adsorption scales with the amount of electron transfer from Fe to O2, which promotes the catalytic activity of C2N-Fe for driving ORR. The nearly linear relationship between the catalytic activity and spin moment variation suggests electronic spin moment as a promising catalytic descriptor for Fe single-atom based catalysts. Following the revealed relationship, the ORR barrier on C2N-Fe was tuned to be as low as 0.10 eV through judicious manipulation of spin states. These findings thus provide important insights into the relationship between catalytic activity and spin, leading to new strategies for designing transition metal single-atom catalysts.

Room temperature coherent control of spin defects in hexagonal boron nitride

Abstract: Optically active spin defects are promising candidates for solid-state quantum information and sensing applications. To use these defects in quantum applications coherent manipulation of their spin state is required. Here, we realize coherent control of ensembles of boron vacancy centers in hexagonal boron nitride (hBN). Specifically, by applying pulsed spin resonance protocols, we measure a spin-lattice relaxation time of 18 microseconds and a spin coherence time of 2 microseconds at room temperature. The spin-lattice relaxation time increases by three orders of magnitude at cryogenic temperature. By applying a method to decouple the spin state from its inhomogeneous nuclear environment the optically detected magnetic resonance linewidth is substantially reduced to several tens of kilohertz. Our results are important for the employment of van der Waals materials for quantum technologies, specifically in the context of high resolution quantum sensing of two-dimensional heterostructures, nanoscale devices, and emerging atomically thin magnets.

Understanding the Mechanism of the Oxygen Evolution Reaction with Consideration of Spin

Abstract: The oxygen evolution reaction (OER) with its intractably high overpotentials is the rate-limiting step in many devices, including rechargeable metal–air batteries, water electrolysis systems and solar fuel devices. Correspondingly, spin state transitions from spin singlet OH–/H2O reactants to spin triplet O2 product have not yet received enough attention. In view of this, this article will discuss electron behaviours during OER by taking into consideration of spin attribute. The main conclusion is that, regardless of the possible adopted mechanisms (the adsorbate evolution mechanism or the lattice oxygen mechanism), the underlying rationale of OER is that three in four electrons being extracted from adsorbates should be in the same spin direction before O=O formation, superimposing high requirements on the spin structure of electrocatalysts. Therefore, upon fully understanding of the OER mechanism with considerations of spin, the awareness of the coupling between spin, charge, orbital and lattice parameters is necessary in the optimization of geometric and electronic structures in transition metal systems. Based on this, this article will discuss the possible dependency of OER efficiency on the electrocatalyst spin configuration, and the relevance of well-recognized factors with spin, including the crystal field, coordination, oxidation, bonding, the eg electron number, conductivity and magnetism. It is hoped that this article will clarify the underlying physics of OER to provide rational guidance for more effective design of energy conversion electrocatalysts.

Ferromagnetic-Antiferromagnetic Coupling Core-Shell Nanoparticles with Spin Conservation for Water Oxidation.

Abstract: Rational design of active oxygen evolution reaction (OER) catalysts is critical for the overall efficiency of water electrolysis. The differing spin states of the OER reactants and products is one of the factors that slows OER kinetics. Thus, spin conservation plays a crucial role in enhancing OER performance. In this work, ferromagnetic (FM)-antiferromagnetic (AFM) Fe3 O4 @Ni(OH)2 core-shell catalysts are designed. The interfacial FM-AFM coupling of these catalysts facilitates selective removal of electrons with spin direction opposing the magnetic moment of FM core, improving OER kinetics. The shell thickness is found critical in retaining the coupling effect for OER enhancement. The magnetic domain structure of the FM core also plays a critical role. With a multiple domain core, the applied magnetic field aligns the magnetic domains, optimizing the electron transport process. A significant enhancement of OER activity is observed for the multiple domain core catalysts. With a single-domain FM core with ordered magnetic dipoles, the spin-selective electron transport with minimal scattering is facilitated even without an applied magnetic field. A magnetism/OER activity model therefore hypothesizes that depends on two main parameters: interfacial spin coupling and domain structure. These findings provide new design principles for active OER catalysts.

Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation.

Abstract: Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well-defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high-spin (dxy 2 dyz 1 dxz 1 d z 2 1 d x 2 - y 2 1 ) to medium-spin (dxy 2 dyz 2 dxz 1 d z 2 1 ), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4 , and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2 . As a result, FeMoPPc with medium-spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high-spin FeN4 and MoPPc with MoN4 , respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.

Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction

Abstract: Single-atom catalysts (SACs) especially supported on two-dimensional nitrogen-doped carbon substrate have been widely reported to be able to effectively promote electrocatalytic N2 reduction reaction (eNRR). The precise design of single-metal-atom active site (SMAS) calls for fundamental understanding of its working mechanism for enhanced eNRR performance. Herein, by means of density functional theory calculations, we theoretically investigate the eNRR performance of nine prototypical SMAS, namely, MN2B2 (M: transition metals of IIIB, IVB and VB groups) which comprises of asymmetric ligands of N2B2 embedded in defective BN nanosheet. Our results reveal the significant role of spin state of SMAS in tuning the potential-determining steps of eNRR, in which MN2B2 site with higher spin magnetic moment (μ) is beneficial to reducing limiting potentials (UL) of eNRR. Specially, CrN2B2 (μ = 4μB), VN2B2 (μ = 3μB) and MoN2B2 (μ = 2μB) demonstrate high activity and selectivity to eNRR. The asymmetric ligands of N2B2 are deemed to be superior over mono-symmetric ligands. More importantly, our results demonstrate that breaking (or deviating) of the scaling relations between key N-containing intermediates (*N2H/*N2 and *NH2/*N2) on MN2B2 can be realized by enhancing spin state of SMAS which renders the active site a balanced N-affinity critical for efficient eNRR. This observation is validated by the calculated Sabatier volcano-shape relation between eNRR limiting potentials and N2 adsorption energy. Our study develops the guidance for catalyst design to boost eNRR performance by tuning the spin state of an active site.

On-Surface Synthesis and Collective Spin Excitations of a Triangulene-Based Nanostar.

Abstract: Triangulene nanographenes are open-shell molecules with predicted high spin state due to the frustration of their conjugated network. Their long-sought synthesis became recently possible over a metal surface. Here, we present a macrocycle formed by six [3]triangulenes, which was obtained by combining the solution synthesis of a dimethylphenyl-anthracene cyclic hexamer and the on-surface cyclodehydrogenation of this precursor over a gold substrate. The resulting triangulene nanostar exhibits a collective spin state generated by the interaction of its 12 unpaired π-electrons along the conjugated lattice, corresponding to the antiferromagnetic ordering of six S=1 sites (one per triangulene unit). Inelastic electron tunneling spectroscopy resolved three spin excitations connecting the singlet ground state with triplet states. The nanostar behaves close to predictions from the Heisenberg model of an S=1 spin ring, representing a unique system to test collective spin modes in cyclic systems.

Controlling dynamic magnetic properties of coordination clusters via switchable electronic configuration

Abstract: Large-sized coordination clusters have emerged as a new class of molecular materials in which many metal atoms and organic ligands are integrated to synergize their properties. As dynamic magnetic materials, such a combination of multiple components functioning as responsive units has many advantages over monometallic systems due to the synergy between constituent components. Understanding the nature of dynamic magnetism at an atomic level is crucial for realizing the desired properties, designing responsive molecular nanomagnets, and ultimately unlocking the full potential of these nanomagnets for practical applications. Therefore, this review article highlights the recent development of large-sized coordination clusters with dynamic magnetic properties. These dynamic properties can be associated with spin transition, electron transfer, and valence fluctuation through their switchable electronic configurations. Subsequently, the article also highlights specialized characterization techniques with different timescales for supporting switching mechanisms, chemistry, and properties. Afterward, we present an overview of coordination clusters (such as cyanide-bridged and non-cyanide assemblies) with dynamic magnetic properties, namely, spin transition and electron transfer in magnetically bistable systems and mixed-valence complexes. In particular, the response mechanisms of coordination clusters are highlighted using representative examples with similar transition principles to gain insights into spin state and mixed-valence chemistry. In conclusion, we present possible solutions to challenges related to dynamic magnetic clusters and potential opportunities for a wide range of intelligent next-generation devices.

Regulating Electronic Spin Moments of Single-Atom Catalyst Sites via Single-Atom Promoter Tuning on S-Vacancy MoS2 for Efficient Nitrogen Fixation.

Abstract: The electrocatalytic activity of transition-metal (TM)-based catalysts is correlated with the spin states of metal atoms. However, developing a way to manipulate spin remains a great challenge. Using first-principles calculations, we first report the crucial role of the spin of exposed Mo atoms around an S-vacancy in the electrocatalytic dinitrogen reduction reaction on defective MoS2 nanosheets and propose a novel strategy for regulating the electronic spin moments by tuning a single-atom promoter (SAP). Single TM atoms adsorbed on a defective MoS2 basal plane serve as SAPs via a noncontact interaction with an exposed Mo active site, inducing a significant spin polarization that promotes N2 adsorption and activation. Interestingly, by changing only the adsorption site of the TM atom, we are able to change the spin moments of the Mo atom, over a wide range of tunable values. The spin moments can be tuned to largely improve the catalytic activity of MoS2 toward the reduction of N2 to NH3.

Electrical read-out of light-induced spin transition in thin film spin crossover/graphene heterostructures

Abstract: Magneto-opto-electronic properties are shown for a hybrid device constructed from a spin crossover (SCO) thin film of a Fe[HB(3,5-(Me)2Pz)3]2 molecular material evaporated over a graphene sensing layer. The principle of electrical detection of the light-induced spin transition in SCO/graphene heterostructures is demonstrated. The switchable spin state of the molecular film is translated into a change of conductance of the graphene channel. The low temperature write/erase process of the conductive remnant states is implemented using two distinct excitation wavelengths, in the red (light-induced spin state trapping, LIESST) region for stabilizing the metastable paramagnetic state, and in the near infrared (reverse-LIESST) region for retrieving the stable diamagnetic state. The bistability of the system is confirmed over a significant temperature window through light-induced thermal hysteresis (LITH). This opens new avenues to study the light-induced spin transition mechanisms exploring the coupling mechanisms between SCO systems and 2D materials, providing electrical readings of the molecules/2D substrate interfaces. These results demonstrate how the electronic states of insulating molecular switches can be stored, read and manipulated by multiple stimuli, while transducing them into low impedance signals, thanks to two-dimensional detectors, revealing the full potential of mixed-dimensional heterostructures for molecular electronics and spintronics.

Switching the magnetic hysteresis of an [Feii–NC–Wv]-based coordination polymer by photoinduced reversible spin crossover

Abstract: Magnetic bistable materials that feature magnetic hysteresis are comparable to elementary binary units and promising for application in switches and memory devices. In this work, we report a material that consists of parallel cyanide-bridged [Feii–Wv] coordination chains linked together through rigid bis(imidazolyl)–benzene ligands and displays multiple magnetic states. The paramagnetic high-spin and diamagnetic low-spin states of the spin-crossover Feii ions can be interconverted by reversible light-induced excited spin state trapping (LIESST) by alternating between light irradiation of 808 and 473 nm. At 1.8 K, under 808-nm-light irradiation, magnetic interactions between the photogenerated paramagnetic high-spin Feii centres and the Wv centres lead to long fragments that exhibit single-chain magnet behaviour, with a wide magnetic hysteresis and a large coercive field of 19 kOe; under a 473 nm light, isolated Feii–Wv fragments behave as single-molecule magnets instead. At 3.3 K, the high-spin form still displays magnetic hysteresis, albeit narrower, whereas the low-spin one does not. Photoinduced spin crossover offers a convenient handle on the spin states and magnetic interactions within a material, which is promising for the development of photoresponsive nanomagnets. Now, a Wv–CN–Feii-based coordination polymer has been prepared that behaves either as a single-chain magnet or as single-molecule magnets under different light irradiations. Its magnetic hysteresis can also be switched on and off.

Guest induced reversible on–off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

Abstract: A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the population γHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0 (state 1) ↔ HS2/3LS1/3 (state 2) ↔ HS1/2LS1/2 (state 3) ↔ HS1/3LS2/3 (state 4) ↔ HS0LS1 (state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {FeII(3,8phen)[Au(CN)2]2}·xPhNO2 (3,8phen = 3,8-phenanthroline, PhNO2 = nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2 guest (x = 1, 1·PhNO2) acts as a molecular wedge between the interpenetrated 3D frameworks via PhNO2-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS–LS⋯ ordering with γHS = 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (with γHS ≈ 2/3) and 4 (with γHS ≈ 1/3), respectively. Below c.a. 20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x = 0, 1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.

A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals

Abstract: Organic radicals are an emerging class of luminophores possessing multiplet spin states and potentially showing spin-luminescence correlated properties. We investigated the mechanism of recently reported magnetic field sensitivity in the emission of a photostable luminescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) doped into host αH-PyBTM molecular crystals. The magnetic field (0–14 T), temperature (4.2–20 K), and the doping concentration (0.1, 4, 10, and 22 wt%) dependence on the time-resolved emission were examined by measuring emission decays of the monomer and excimer. Quantum mechanical simulations on the decay curves disclosed the role of the magnetic field; it dominantly affects the spin sublevel population of radical dimers in the ground states. This situation is distinctly different from that in conventional closed-shell luminophores, where the magnetic field modulates their excited-state spin multiplicity. Namely, the spin degree of freedom of ground-state open-shell molecules is a new key for achieving magnetic-field-controlled molecular photofunctions.

Five-second coherence of a single spin with single-shot readout in silicon carbide

Abstract: An outstanding hurdle for defect spin qubits in silicon carbide (SiC) is single-shot readout - a deterministic measurement of the quantum state. Here, we demonstrate single-shot readout of single defects in SiC via spin-to-charge conversion, whereby the defect's spin state is mapped onto a long-lived charge state. With this technique, we achieve over 80% readout fidelity without pre- or post-selection, resulting in a high signal-to-noise ratio (SNR) that enables us to measure long spin coherence times. Combined with pulsed dynamical decoupling sequences in an isotopically purified host material, we report single spin T2 > 5s, over two orders of magnitude greater than previously reported in this system. The mapping of these coherent spin states onto single charges unlocks both single-shot readout for scalable quantum nodes and opportunities for electrical readout via integration with semiconductor devices.

Photogenerated Spin-Correlated Radical Pairs: From Photosynthetic Energy Transduction to Quantum Information Science.

Abstract: More than a half century ago, the NMR spectra of diamagnetic products resulting from radical pair reactions were observed to have strongly enhanced absorptive and emissive resonances. At the same time, photogenerated radical pairs were discovered to exhibit unusual electron paramagnetic resonance spectra that also had such resonances. These non-Boltzmann, spin-polarized spectra were observed in both chemical systems as well as in photosynthetic reaction center proteins following photodriven charge separation. Subsequent studies of these phenomena led to a variety of chemical electron donor-acceptor model systems that provided a broad understanding of the spin dynamics responsible for these spectra. When the distance between the two radicals is restricted, these observations result from the formation of spin-correlated radical pairs (SCRPs) in which the spin-spin exchange and dipolar interactions between the two unpaired spins play an important role in the spin dynamics. Early on, it was recognized that SCRPs photogenerated by ultrafast electron transfer are entangled spin pairs created in a well-defined spin state. These SCRPs can serve as spin qubit pairs (SQPs), whose spin dynamics can be manipulated to study a wide variety of quantum phenomena intrinsic to the field of quantum information science. This Perspective highlights the role of SCRPs as SQPs, gives examples of possible quantum manipulations using SQPs, and provides some thoughts on future directions.

A Fluorescence-Detected Coordination-Induced Spin State Switch.

Abstract: The response of the spin state to in situ variation of the coordination number (CISSS) is a promising and viable approach to smart sensor materials, yet it suffers to date from insensitive detection. Herein, we present the synthetic access to a family of planar nickel(II) complexes, whose CISSS is sensitively followed by means of fluorescence detection. For this purpose, nickel(II) complexes with four phenazine-based Schiff base-like ligands were synthesized and characterized through solution-phase spectroscopy (NMR and UV-vis), solid-state structure analysis (single-crystal XRD), and extended theoretical modeling. All of them reveal CISSS in solution through axial ligating a range of N- and O-donors. CISSS correlates nicely with the basicity of the axial ligand and the substitution-dependent acidity of the nickel(II) coordination site. Remarkably, three out of the four nickel(II) complexes are fluorescent in noncoordinating solvents but are fluorescence-silent in the presence of axial ligands such as pyridine. As these complexes are rare examples of fluorescent nickel(II) complexes, the photophysical properties with a coordination number of 4 were studied in detail, including temperature-dependent lifetime and quantum yield determinations. Most importantly, fluorescence quenching upon adding axial ligands allows a "black or white", i.e. digital, sensoring of spin state alternation. Our studies of fluorescence-detected CISSS (FD-CISSS) revealed that absorption-based CISSS and FD-CISSS are super proportional with respect to the pyridine concentration: FD-CISSS features a higher sensitivity. Overall, our findings indicate a favored ligation of these nickel(II) complexes in the excited state in comparison to the ground state.

Room temperature conductance switching in a molecular iron(III) spin crossover junction

Abstract: Herein, we report the first room temperature switchable Fe(III) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [FeIII(qsal-I)2]NTf2 (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current–voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule—electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds.

Itinerant ferromagnetism mediated by giant spin polarization of the metallic ligand band in the van der Waals magnet Fe 5 Ge Te 2

Abstract: We investigate near-Fermi-energy (${E}_{F}$) element-specific electronic and spin states of ferromagnetic van der Waals (vdW) metal ${\mathrm{Fe}}_{5}\mathrm{Ge}{\mathrm{Te}}_{2}$. The soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) measurement provides spectroscopic evidence of localized Fe $3d$ band. We also find prominent hybridization between the localized Fe $3d$ band and the delocalized Ge/Te $p$ bands. This picture is strongly supported from direct observation of the remarkable spin polarization of the ligand $p$ bands near ${E}_{F}$, using x-ray magnetic circular dichroism (XMCD) measurements. The strength of XMCD signal from ligand element Te shows the highest value, as far as we recognize, among literature reporting finite XMCD signal for nonmagnetic element in any systems. Combining SX-ARPES and elemental selective XMCD measurements, we collectively point to an important role of giant spin polarization of the delocalized ligand Te states for realizing itinerant long-range ferromagnetism in ${\mathrm{Fe}}_{5}\mathrm{Ge}{\mathrm{Te}}_{2}$. Our finding provides a fundamental elemental selective viewpoint for understanding mechanism of itinerant ferromagnetism in low-dimensional compounds, which also leads to insight for designing exotic magnetic states by interfacial band engineering in heterostructures.

Electronic and magnetic properties of graphene quantum dots doped with alkali metals

Abstract: The electronic and magnetic properties of armchair-hexagonal (AHEX) and zigzag-triangular (ZTRI) graphene quantum dots doped with alkali metals are investigated using density functional theory The binding energy confirms the stability of the undoped systems Although doping decreases stability of single layer structures, in bilayer ones the binding energy between the layers increases The former is due to the broken bonds and the deformation at the surface, while the later is due to the chemical bonds formation between the layers We found that the lowest ground state energy for AHEX/AHEX-doped is the singlet/quadruplet spin state Therefore, AHEX dots experience transformation from diamagnetic to ferromagnetic state after doping In addition, the optimized spin state for ZTRI/ZTRI-doped is the quintet/sextet spin-polarized state In few cases, the doped AHEX/ZTRI dots have doublet/quadruplet spin state due to the strong interaction between the flake atoms that passivates some unpaired electrons Magnetic properties depend also on stacking, for instance pristine bilayer triangular flakes become antiferromagnetic due to pairing between edge states The energy gap significantly affected by doping, for instance the gap decreases from ~37 eV in hexagonal flakes to 15 eV when it is doped with Na in the upper position Electrons from the broken bonds around the doped metal form orbitals loosely bound to the flake consequently decreasing the energy gap On the other hand, stacking increases the energy gap in bilayer triangular flakes due to the mutual passivation of the reactive edge states from both the layers The calculated spin up/down density ratio is high in hexagonal flakes leading to high spin polarization (P), for instance P = 064 in hexagonal flakes doped with K atom The found enhanced spin polarization, in addition to the tunable magnetic properties, makes doped graphene flakes promising candidates for spintronic devices

Broad-band spectroscopy of a vanadyl porphyrin: a model electronuclear spin qudit.

Abstract: We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9–10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the ‘1’ and ‘0’ basis states. For lower magnetic fields (B < 0.1 T), and lower frequencies (<2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.

DFT studies of single and multiple alkali metals doped C24 fullerene for electronics and nonlinear optical applications.

Abstract: The geometric, electronic and nonlinear properties of exohedral and endohedral single and multiple alkali metal (Li, Na and K) atom doped C24 fullerene are studied. First, the most stable orientations at the most stable spin state are evaluated. Complexes with odd metal atoms are stable at doublet spin state and complexes with even number of metal atoms are stable at singlet spin state. Thermodynamic analysis shows that Li4C24 among all complexes with highest thermodynamic stability has interaction energy of −190.78 kcal mol−1. The energy gaps (GH-L) are fairly reduced in single and multi-doped cages, and the lowest energy gap is observed for K4C24 complex. NBO analysis is performed to validate the charge transfer from alkali metal toward C24. The largest amount of charge (0.95 |e|) transfer is monitored in exohedral K2C24 complex where the highest charge transfer is for potassium (K) metal. Total density of states (TDOS) spectra of doped complexes justify the involvement of alkali metals and nanocage in new HOMO formation for the excess electrons. First hyperpolarizability is descriptor of NLO properties of single and multi-doped complexes are calculated. It is observed that doping of alkali metal atoms (Li, Na and K) greatly enhances the first hyperpolarizability. Among all the complexes of C24, Na3C24 shows the highest hyperpolarizability value of 2.74 × 105 au. The results of this study are a guideline for the computational designing of highly efficient and thermodynamically stable complexes for the optical and optoelectronic technologies.

Active terahertz spin state and optical chirality in liquid crystal chiral metasurface

Abstract: Dynamic control of photonic spin state and chirality plays a vital role in various applications, such as polarization control, polarization-sensitive imaging, and biosensing. Here, we present a scheme for the flexible and dynamic manipulation of terahertz spin state conversion and optical chirality by combining two achiral structures: an asymmetric metasurface and a layer of anisotropic liquid crystal. The proposed asymmetric metasurface can realize the polarization conversion effect. For the circularly polarized incidence, it exhibits the asymmetric transmission of the spin-flipped states but no spin-locked optical chirality since its geometry is mirror symmetric along with the wave propagation. The introduction of the liquid crystal makes the composite metasurface not only exhibit the spin state conversion but also spin-locked chirality and spin-flipped chirality on account of breaking mirror symmetry, which realizes an electrically active terahertz chiral device. The experimental results show that the asymmetric transmission of the terahertz spin states can be dynamically manipulated, resulting in a large controllable range 83.8% to \ensuremath{-}30.7% of spin-locked circular dichroism at 0.76 THz and \ensuremath{-}98.2% to 44.7% of spin-flipped circular dichroism at 0.73 THz. This work paves the way for the development of terahertz meta devices capable of enabling active photonic spin state and chirality manipulation.

Co-based molecular catalysts for efficient CO2 reduction via regulating spin states

Abstract: A typical mode of CO2 activation is that d electrons at the d orbital of transition metals transfer to the unoccupied π* orbital of CO2. Thus the exploration of the relationship between d-electron behaviors and CO2 activation is of great importance. Herein, we demonstrate that high-spin state of 3d electrons in Co2+ facilitated the activation of CO2 over Co-salophen-X (X represents to Cl, Br, or I). Among these catalysts, Co-salophen-Br exhibited the highest Faradaic efficiency for CO. Notably, the Faradaic efficiency for CO over Co-salophen-Br reached 98.5 % at −0.70 V versus reversible hydrogen electrode, which was 1.5 and 1.2 times as high as those over Co-salophen-Cl (64.8 %) and Co-salophen-I (81.8 %), respectively. Density functional theory calculations revealed that high-spin state of Co sites decreased the reaction energy barrier for the formation of CO. Based on the analysis of electronic state, the ratio of high-spin state was 65.6 % for Co-salophen-Br, which was the highest among the three Co-based molecules. The Co sites with high-spin state promoted the electron transfer from high-energy 3d orbital (3dz2 and 3dx2-y2) of Co to the unoccupied π* orbital of CO2, improving catalytic performance.

Tunable high-temperature itinerant antiferromagnetism in a van der Waals magnet

Abstract: Discovery of two dimensional (2D) magnets, showing intrinsic ferromagnetic (FM) or antiferromagnetic (AFM) orders, has accelerated development of novel 2D spintronics, in which all the key components are made of van der Waals (vdW) materials and their heterostructures. High-performing and energy-efficient spin functionalities have been proposed, often relying on current-driven manipulation and detection of the spin states. In this regard, metallic vdW magnets are expected to have several advantages over the widely-studied insulating counterparts, but have not been much explored due to the lack of suitable materials. Here, we report tunable itinerant ferro- and antiferromagnetism in Co-doped Fe4GeTe2 utilizing the vdW interlayer coupling, extremely sensitive to the material composition. This leads to high TN antiferromagnetism of TN ~ 226 K in a bulk and ~210 K in 8 nm-thick nanoflakes, together with tunable magnetic anisotropy. The resulting spin configurations and orientations are sensitively controlled by doping, magnetic field, and thickness, which are effectively read out by electrical conduction. These findings manifest strong merits of metallic vdW magnets as an active component of vdW spintronic applications. Metallic van der Waals magnets have considerable technological promise, due to their ability to be strongly coupled with electronic currents and integrated in two dimensional heterostructures. Here, Seo et al. demonstrate highly tunable itinerant antiferromagnetism in a van der Waals magnet.

Highly Degenerate Ground States in a Frustrated Antiferromagnetic Kagome Lattice in a Two-Dimensional Metal-Organic Framework.

Abstract: Realization of the Kagome antiferromagnetic (KAF) lattice is of high interest because the geometric frustration in the Kagome lattice is expected to give rise to highly degenerated ground states that may host exotic phases such as quantum spin liquid. Here we demonstrate the design and synthesis of a single-layer two-dimensional metal-organic framework (2D-MOF) containing a Kagome lattice of Fe(II) ions assembled on a Au(111) surface. First-principles calculations reveal that the Fe(II) ions are at a high spin state of S = 2 and are coupled antiferromagnetically with nearest-neighboring exchange J1 = 5.8 meV. The ground state comprises various degenerated spin configurations including the well-known q = 0 and q = √3 × √3 phases. Remarkably, we observe a spin excitation at 6 meV using tunneling spectroscopy. This work points out a feasible route toward realizing spin 1/2 KAF, a candidate quantum spin liquid system, by replacing Fe(II) by Cu(II) in the same structure.

Absence of heating in a uniform Fermi gas created by periodic driving.

Abstract: Ultracold atoms are a powerful resource for quantum technologies. As such, they are usually confined in an external potential that often depends on the atomic spin, which may lead to inhomogeneous broadening, phase separation and decoherence. Dynamical decoupling provides an approach to mitigate these effects by applying an external field that induces rapid spin rotations. However, a continuous periodic driving of a generic interacting many-body system eventually heats it up. The question is whether dynamical decoupling can be applied at intermediate times without altering the underlying physics. Here we answer this question affirmatively for a strongly interacting degenerate Fermi gas held in a flat box-like potential. We counteract most of the gravitational force by applying an external magnetic field with an appropriate gradient. Since the magnetic force, and consequently, the whole potential, is spin-dependent, we employ rf to induce a rapid spin rotation. The driving causes atoms in both spin states to experience the same time-average flat potential, leading to a uniform cloud. Most importantly, we find that when the driving frequency is high enough, there is no heating on experimentally relevant timescales, and physical observables are similar to those of a stationary gas. In particular, we measure the pair-condensation fraction of a fermionic superfluid at unitarity and the contact parameter in the BEC-BCS crossover. The condensate fraction exhibits a non-monotonic dependence on the drive frequency and reaches a value higher than its value without driving. The contact agrees with recent theories and calculations for a uniform stationary gas. Our results establish that a strongly-interacting quantum gas can be dynamically decoupled from a spin-dependent potential for long periods of time without modifying its intrinsic many-body behavior.

Exploring Photogenerated Molecular Quartet States as Spin Qubits and Qudits.

Abstract: Photogenerated molecular spin systems hold great promise for applications in quantum information science because they can be prepared in well-defined spin states at modest temperatures, they often exhibit long coherence times, and their properties can be tuned by chemical synthesis. Here, we investigate a molecular spin system composed of a 1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) chromophore covalently linked to a stable nitroxide radical (TEMPO) by optical and electron paramagnetic resonance (EPR) techniques. Upon photoexcitation of the spin system, a quartet state is formed as confirmed by transient nutation experiments. This quartet state has spin polarization lifetimes longer than 0.1 ms and is characterized by relatively long coherence times of ∼1.8 μs even at 80 K. Rabi oscillation experiments reveal that more than 60 single-qubit logic operations can be performed with this system at 80 K. The large magnitude of the nitroxide 14N hyperfine coupling in the quartet state of PDI-TEMPO is resolved in the transient EPR spectra and leads to a further splitting of the quartet state electron spin sublevels. We discuss the properties of this photogenerated multilevel system, comprising 12 electron-nuclear spin states, in the context of its viability as a qubit for applications in quantum information science.

Spin Emitters beyond the Point Dipole Approximation in Nanomagnonic Cavities

Abstract: Control over transition rates between spin states of emitters is crucial in a wide variety of fields ranging from quantum information science to the nanochemistry of free radicals. We present an ap...

Resolution of Low-Energy States in Spin-Exchange Transition-Metal Clusters: Case Study of Singlet States in [Fe(III)4S4] Cubanes.

Abstract: Polynuclear transition-metal (PNTM) clusters owe their catalytic activity to numerous energetically low-lying spin states and stable oxidation states. The characterization of their electronic structure represents one of the greatest challenges of modern chemistry. We propose a theoretical framework that enables the resolution of targeted electronic states with ease and apply it to two [Fe(III)4S4] cubanes. Through direct access to their many-body wave functions, we identify important correlation mechanisms and their interplay with the geometrical distortions observed in these clusters, which are core properties in understanding their catalytic activity. The simulated magnetic coupling constants predicted by our strategy allow us to make qualitative connections between spin interactions and geometrical distortions, demonstrating its predictive power. Moreover, despite its simplicity, the strategy provides magnetic coupling constants in good agreement with the available experimental ones. The complexes are intrinsically frustrated anti-ferromagnets, and the obtained spin structures together with the geometrical distortions represent two possible ways to release spin frustration (spin-driven Jahn-Teller distortion). Our paradigm provides a simple, yet rigorous, route to uncover the electronic structure of PNTM clusters and may be applied to a wide variety of such clusters.