Copper Spins Research Articles

Large-bipolaron liquids in cuprate superconductors.

Uniquely, large-bipolarons' self-trapped holes occupy superoxygens, each comprising four oxygens circumscribed by four coppers in a CuO2 plane, formed as oxygens relax inward and coppers relax outward. Critically, concomitant oxygen-to-copper electron transfer eliminates copper spins. The d-symmetry of superoxygens' ground state molecular orbital tracks the superoxygens' predominant zero-point radial vibrations. These large bipolarons' distinctive charge transport, absorption, magnetism, local atomic vibrations, condensation into a liquid, and subsequent superconductivity are consistent with cuprate superconductors' long-established unusual properties.

In One Fell Sweep: Modeling Exchange, Hyperfine and Dipolar Interactions from EPR Spectra of Copper(II) Spin Triangles

The weak intramolecular magnetic interactions within a series of CuII3 complexes based on the trinucleating 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (dipyatriz) ligand were investigated via Electron Paramagnetic Resonance (EPR) spectroscopy. X- and Q-band EPR spectroscopy in powders and frozen solutions were recorded and the Q-band spectra were interpreted by a multispin Hamiltonian model comprising exchange, dipolar and hyperfine interactions. The described methodology is suitable for the elucidation of weak intramolecular interactions which are not amenable to analysis via magnetic susceptibility studies.

On the Theory of Magnetoelectric Coupling in LiCu2O2

A microscopic theory is proposed for coupling of copper spins with an external electric field in the magnetically ordered phase of LiCu2O2. The expressions are derived for the dipole moment components of exchange-coupled pairs of copper spins, as well as expressions for describing the macroscopic polarization in terms of the angles determining spatial orientations of spin rotation planes (helixes) in copper bichains. It is shown that zero electric polarization in isostructural compound NaCu2O2 can be explained by the difference in the spin structures in NaCu2O2 and LiCu2O2.

Feasibility of imaging in nuclear magnetic resonance force microscopy using Boltzmann polarization

We report on magnetic resonance force microscopy measurements of the Boltzmann polarization of nuclear spins in copper by detecting the frequency shift of a soft cantilever. We use the time-dependent solution of the Bloch equations to derive a concise equation describing the effect of radio-frequent (RF) magnetic fields on both on- and off-resonant spins in high magnetic field gradients. We then apply this theory to saturation experiments performed on a 100 nm thick layer of copper, where we use the higher modes of the cantilever as a source of the RF field. We demonstrate a detection volume sensitivity of only (40nm)3, corresponding to about 1.6×104 polarized copper nuclear spins. We propose an experiment on protons where, with the appropriate technical improvements, frequency-shift based magnetic resonance imaging with a resolution better than (10nm)3 could be possible. Achieving this resolution would make imaging based on the Boltzmann polarization competitive with the more traditional stochastic spin-fluctuation based imaging, with the possibility to work at millikelvin temperatures.

Importance of spin current generation and detection by spin injection and the spin Hall effect for lateral spin valve performance

Lateral spin valves are attractive device geometries where functional spin currents can be generated and detected by various mechanisms, such as spin injection and the direct and the inverse spin Hall effect. To understand the mechanisms behind these effects better, as well as their potential for application in devices, we combine multiple mechanisms in multi-terminal Pt–Py–Cu lateral spin valves: we generate pure spin currents in the copper spin conduit both via the spin Hall effect in platinum and electric spin injection from permalloy and detect signals both via conventional non-local detection and via the inverse spin Hall effect in the same device at variable temperatures. Differences are observed, which we explain by the different spin injection and detection mechanisms, revealing their importance for the temperature dependence, which is not just governed by the spin transport in the conduit as previously claimed. By determining a different sensitivity of the observed effects on the interfaces, we highlight the importance of the exact current path for the device operation.

Effect of different in-chain impurities on the magnetic properties of the spin chain compound SrCuO2 probed by NMR

The S=1/2 Heisenberg spin chain compound SrCuO2 doped with different amounts of nickel (Ni), palladium (Pd), zinc (Zn) and cobalt (Co) has been studied by means of Cu nuclear magnetic resonance (NMR). Replacing only a few of the S=1/2 Cu ions with Ni, Pd, Zn or Co has a major impact on the magnetic properties of the spin chain system. In the case of Ni, Pd and Zn an unusual line broadening in the low temperature NMR spectra reveals the existence of an impurity-induced local alternating magnetization (LAM), while exponentially decaying spin-lattice relaxation rates $T_1^{-1}$ towards low temperatures indicate the opening of spin gaps. A distribution of gap magnitudes is proven by a stretched spin-lattice relaxation and a variation of $T_1^{-1}$ within the broad resonance lines. These observations depend strongly on the impurity concentration and therefore can be understood using the model of finite segments of the spin 1/2 antiferromagnetic Heisenberg chain, i.e. pure chain segmentation due to S = 0 impurities. This is surprising for Ni as it was previously assumed to be a magnetic impurity with S = 1 which is screened by the neighboring copper spins. In order to confirm the S = 0 state of the Ni, we performed x-ray absorption spectroscopy (XAS) and compared the measurements to simulated XAS spectra based on multiplet ligand-field theory. Furthermore, Zn doping leads to much smaller effects on both the NMR spectra and the spin-lattice relaxation rates, indicating that Zn avoids occupying Cu sites. For magnetic Co impurities, $T_1^{-1}$ does not obey the gap like decrease, and the low-temperature spectra get very broad. This could be related to the increase of the Neel temperature which was observed by recent muSR and susceptibility measurements, and is most likely an effect of the impurity spin $S\neq0$.

Theoretical investigation of electronic, magnetic, transport and optical properties of the pure and doped cuprate superconductor HgBa2CuO4+δ

We report detailed DFT calculations and Monte Carlo simulations on the pure and doped cuprate superconductor HgBa2CuO4+δ. For the pure compound (δ = 0), we have obtained an insulating behavior with strong antiferromagnetic copper spin correlations in the CuO2 plane. The high value of the calculated Néel temperature TN = 333 K reflects the large in-plane exchange interaction J = -145 meV. The obtained optical properties and critical exponents demonstrate the anisotropic quasi-2D character of this type of materials. As for the doped compound the electronic structure and the transport properties have been investigated for various values of doping. Based on these data, we suggest a prediction of the value of optimum doping for HgBa2CuO4+δ(δoptimal = 0.125).

First coordination polymer based on diterpenoids. Synthesis, structure, and magnetic properties

One-dimensional coordination polymer was obtained by cation exchange reaction of triethylammonium salt of methyl ent-16α-H-phosphonyloxybeyeran-19-oate with CuCl2. Its structure was determined by single crystal X-ray diffraction analysis. The formation of hydrophilic channels consisting of phosphorus containing fragments, copper atoms, and water, which are framed by hydrophobic surroundings from tetracyclic bulky beyeran substituents, is observed in the crystal. The study of the temperature dependence of the static magnetic susceptibility of the polymer indicates a weak antiferromagnetic interaction between the copper spins.

On collective spin excitations in electron doped cuprate high-temperature superconductors

An analytical formula with three-center terms has been proposed for the calculation of the dynamic spin susceptibility of electron-doped cuprates. The results of the calculation of the imaginary part of the susceptibility reproduce the main features of inelastic neutron scattering and resonant inelastic X-ray scattering. It has been shown that the high-frequency behavior of the dispersion of collective spin excitations is mainly determined by the parameters of the conduction band and hardly depends on the exchange coupling of copper spins. The spin and superconducting gap parameters, as well as correlation effects associated with the three-center terms, play the determining role in the formation of the spin response in the region Q ≈ (π, π).

Tellurium-bridged two-leg spin ladder inBa2CuTeO6

We present single-crystal growth and magnetic property studies of tellurium-bridged copper spin-$\frac{1}{2}$ system ${\mathrm{Ba}}_{2}{\mathrm{CuTeO}}_{6}$. The spin-exchange interaction among copper spins via $\mathrm{Cu}\text{\ensuremath{-}}\mathrm{O}\text{\ensuremath{-}}\mathrm{Te}\text{\ensuremath{-}}\mathrm{O}\text{\ensuremath{-}}\mathrm{Cu}$ super-superexchange route leads to a novel two-leg spin ladder system. Spin susceptibility $\ensuremath{\chi}(T)$ data indicate that the triclinic ${\mathrm{Ba}}_{2}{\mathrm{CuTeO}}_{6}$ undergoes a stepwise crossover for exchange couplings revealed by a broad maximum of $\ensuremath{\chi}(T)$ near ${T}_{max}\ensuremath{\sim}75$ K and an anisotropic cusp in $\frac{d\ensuremath{\chi}}{dT}(T)$ at ${T}_{N}\ensuremath{\sim}15$ K to signify a three-dimensional (3D) antiferromagnetic long-range ordering (LRO). The 3D LRO has been suggested from the anisotropic behavior of $\ensuremath{\chi}(T)$ with strong $c$-axis spin anisotropy and the signature of spin-flop transition from the isothermal magnetization below ${\mathit{T}}_{N}$. Analysis of magnetic heat capacity (${C}_{m}$) at ${T}_{N}\ensuremath{\sim}15$ K indicates that most of the spin entropy $(\ensuremath{\sim}92%)$ has already been released above ${T}_{N}$, which supports the picture of consecutive spin entropy reduction upon cooling with Te-bridged two-leg spin ladder system with strong intraladder and interladder couplings. Theoretical $\mathrm{DFT}+U$ calculations have been performed to search for the ground-state magnetic configuration and also to evaluate exchange-coupling constants that support the magnetic model deduced from the combined spin susceptibility and crystal structure symmetry analysis.

Probing the Dipolar Coupling in a Heterospin Endohedral Fullerene-Phthalocyanine Dyad.

Paramagnetic endohedral fullerenes and phthalocyanine (Pc) complexes are promising building blocks for molecular quantum information processing, for which tunable dipolar coupling is required. We have linked these two spin qubit candidates together and characterized the resulting electron paramagnetic resonance properties, including the spin dipolar coupling between the fullerene spin and the copper spin. Having interpreted the distance-dependent coupling strength quantitatively and further discussed the antiferromagnetic aggregation effect of the CuPc moieties, we demonstrate two ways of tuning the dipolar coupling in such dyad systems: changing the spacer group and adjusting the solution concentration.

Redox noninnocence of the bridge in copper(II) salophen and bis(oxamato) complexes.

Two square-planar copper(II) complexes of 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis(dimethylamino)benzene (1) and N-[4,5-bis(dimethylamino)-2-(oxalylamino)benzene]oxamate (2(2-)) were prepared. The crystal structures of the proligands H2L(1) and Et2H2L(2), as well as the corresponding complexes, are reported. The proligands each display a one-electron-oxidation wave, which is assigned to oxidation of the bis(dimethylamino)benzene moiety into a π radical. Complexes 1 and 2(2-) exhibit reversible one-electron-oxidation waves in their cyclic voltammograms (E1/2(1) = 0.14 and E1/2(2) = 0.31 V for 1 and E1/2(1) = -0.47 V vs Fc(+)/Fc for 2(2-)). The first process corresponds to oxidation of the bis(dimethylamino)benzene central ring into a π radical, while the second process for 1 is ascribed to oxidation of the π radical into an α-diiminoquinone. The one-electron-oxidized species 1(+) and 2(-) exhibit intense visible-near-IR absorptions, which are diagnostic of π radicals. They display a triplet signal in their electron paramagnetic resonance spectra, which stem from magnetic coupling between the ligand-radical spin and the copper(II) spin. The zero-field-splitting parameters are larger for 2(-) than 1(+) because of greater delocalization of the spin density onto the coordinated amidato N atoms. Density functional theory calculations support a π-radical nature of the one-electron-oxidized complexes, as well as S = 1 ground spin states. The electrogenerated 1(2+) comprises a closed-shell diiminoquinone ligand coordinated to a copper(II) metal center. Both 1 and 2 catalyze the aerobic oxidation of benzyl alcohol, albeit with different yields.

Magnetic Orderings in Li2Cu(WO4)2 with Tungstate-Bridged Quasi-1D Spin-1/2 Chains.

By both experimental measurements and theoretical calculations, we investigated the magnetic and electronic properties of Li2Cu(WO4)2 as a tungstate-bridged quasi-one-dimensional (1D) copper spin-(1/2) chain system. Interestingly, magnetic susceptibility χ(T) and specific heat measurements show that the system undergoes a three-dimensional antiferromagnetic (AF)-like ordering at TN ≈ 3.7 K, below a broad χ(T) maximum at ∼8.9 K indicating a low-dimensional short-range AF spin correlation. Bonner-Fisher model fitting of χ(T) leads to an AF intrachain exchange constant of J/kB = 15.8 ± 0.1 K, and mean-field theory estimation gives an interchain coupling constant of J⊥/kB = 1.6 K, which supports the quasi-1D nature of this spin system. Theoretical evaluation of exchange coupling constants within the generalized gradient approximation (GGA) plus on-site Coulomb interaction (U) shows that the dominant AF exchange interaction is of ∼13.9 K along the a-axis with weak interchain coupling, in agreement with the experimental result of a quasi-1D spin-(1/2) chain system. The GGA+U calculations also predict that Li2Cu(WO4)2 is a charge transfer-type AF semiconductor with a direct band gap of 1.5 eV.

FTIR study of thermally induced magnetostructural transitions in breathing crystals.

"Breathing crystals" based on copper(II) hexafluoroacetylacetonates and pyrazolyl-substituted nitronyl nitroxides comprise the exchange-coupled clusters within the polymeric chains. Owing to an interplay of exchange interaction between copper(II) and nitroxide spins and Jahn-Teller nature of copper(II) complex, the breathing crystals demonstrate thermally and light-induced magnetostructural transitions in many aspects similar to the classical spin crossover. Herewith, we report the first application of variable temperature (VT) far/mid Fourier transform infrared (FTIR) spectroscopy and mid FTIR microscopy to breathing crystals. This VT-FTIR study was aimed toward clarification of the transitions mechanism previously debated on the basis of superconducting quantum interference device, X-ray diffraction, and electron paramagnetic resonance data. VT-FTIR showed the onset of new vibrational bands during phase transitions occurring at the expense of several existing ones, whose intensity was significantly reduced. The most pronounced spectral changes were assigned to corresponding vibrational modes using quantum chemical calculations. A clear-cut correlation was found between temperature-dependent effective magnetic moment of studied compounds and the observed VT-FTIR spectra. Importantly, VT-FTIR confirmed coexistence of two types of copper(II)-nitroxide clusters during gradual magnetostructural transition. Such clusters correspond to weakly coupled and strongly coupled spin states, whose relative contribution depends on temperature. The pronounced difference in the VT-FTIR spectra of two states in breathing crystals is a fingerprint of magnetostructural transition, and understanding of these characteristics achieved by us will be useful for future studies of breathing crystals as well as their diamagnetic analogues.

Effect of electron correlation on the electronic structure and spin-lattice coupling of high-Tccuprates: Quantum Monte Carlo calculations

Electron correlation effects are particularly strong in the high temperature superconducting materials. Devising an accurate description of these materials has long been a challenge, with these strong correlation effects historically being considered impossible or impractical to simulate computationally. Using quantum Monte Carlo techniques, we have explicitly simulated electron correlations in several cuprate materials from first principles. These simulations accurately reproduce many important physical quantities about these materials, including the interaction-induced gap and the superexchange coupling between copper spins, with no additional parameters beyond fundamental constants. We further investigate the dimensionless spin-lattice coupling parameter in the parent materials, showing that it varies dramatically between 0.1 and 1.0 depending on the interlayer. This result indicates that the lattice and magnetic degrees of freedom are not independent in these systems, which may have ramifications for the origin of superconductivity.

Nematic and spin-charge orders driven by hole-doping a charge-transfer insulator

Recent experimental discoveries have brought a diverse set of broken symmetry states to the center stage of research on cuprate superconductors. Here, we focus on a thematic understanding of the diverse phenomenology by exploring a strong-coupling mechanism of symmetry breaking driven by frustration of antiferromagnetic (AFM) order. We achieve this through a variational study of a three-band model of the CuO2 plane with Kondo type exchange couplings between doped oxygen holes and classical copper spins. Two main findings from this strong-coupling multi-band perspective are (1) that the symmetry hierarchy of spin stripe, charge stripe, intra-unit-cell nematic order and isotropic phases are all accessible microscopically within the model, (2) many symmetry-breaking patterns compete with energy differences within a few meV per Cu atom to produce a rich phase diagram. These results indicate that the diverse phenomenology of broken-symmetry states in hole-doped AFM charge-transfer insulators may indeed arise from hole-doped frustration of antiferromagnetism.

New Routes to Synthesizing an Ordered Perovskite CaCu3Fe2Sb2O12 and Its Magnetic Structure by Neutron Powder Diffraction

The search for new double-perovskite oxides has grown rapidly in recent years because of their interesting physical properties like ferroelectricity, magnetism, and multiferroics. The synthesis of double perovskites, especially the A-site-ordered perovskites, in most cases needs to be made under high pressure, which is a drawback for applying these materials. Here we have demonstrated synthetic routes at ambient pressure by which we have obtained a high-quality duo-sites-ordered double perovskite, CaCu3Fe2Sb2O12, which has been previously synthesized under high pressure. The availability of a large quantity of the powder sample allows us to determine the crystal and magnetic structures by neutron powder diffraction (NPD) at 300 and 1.3 K. Measurements of the magnetization and heat capacity showed a ferrimagnetic transition at 160 K. A ferrimagnetic structure consisting of the uncompensated antiferromagnetic coupling between neighboring collinear copper and iron spins has been resolved from the low-temperature NPD data.

Adiabatic and fast passage ultra-wideband inversion in pulsed EPR

We demonstrate that adiabatic and fast passage ultra-wideband (UWB) pulses can achieve inversion over several hundreds of MHz and thus enhance the measurement sensitivity, as shown by two selected experiments. Technically, frequency-swept pulses are generated by a 12 GS/s arbitrary waveform generator and upconverted to X-band frequencies. This pulsed UWB source is utilized as an incoherent channel in an ordinary pulsed EPR spectrometer. We discuss experimental methodologies and modeling techniques to account for the response of the resonator, which can strongly limit the excitation bandwidth of the entire non-linear excitation chain. Aided by these procedures, pulses compensated for bandwidth or variations in group delay reveal enhanced inversion efficiency. The degree of bandwidth compensation is shown to depend critically on the time available for excitation. As a result, we demonstrate optimized inversion recovery and double electron electron resonance (DEER) experiments. First, virtually complete inversion of the nitroxide spectrum with an adiabatic pulse of 128ns length is achieved. Consequently, spectral diffusion between inverted and non-inverted spins is largely suppressed and the observation bandwidth can be increased to increase measurement sensitivity. Second, DEER is performed on a terpyridine-based copper (II) complex with a nitroxide-copper distance of 2.5nm. As previously demonstrated on this complex, when pumping copper spins and observing nitroxide spins, the modulation depth is severely limited by the excitation bandwidth of the pump pulse. By using fast passage UWB pulses with a maximum length of 64ns, we achieve up to threefold enhancement of the modulation depth. Associated artifacts in distance distributions when increasing the bandwidth of the pump pulse are shown to be small.

Effect of paramagnetic Mn ion on the superconductivity of Cu0.5Tl0.5Ba2Ca2−xMnxCu3O10−y

The Mn-doped Cu0.5Tl0.5Ba2(Ca2−xMnx)Cu3O10−y(x = 0, 0.15, 0.25, 0.35, 0.5, 0.75 1.0, and 1.25) superconductor samples were prepared at atmospheric pressure using solid state reaction method. The objectives of Mn doping at the Ca site were to improve the inter plane coupling and to see the effect of paramagnetic Mn atom on copper spins in the CuO2 planes and in turn on superconductivity in the light of charge stripe theory. The Mn doped samples have orthorhombic structure and the cell parameters were decreased after the increase of Mn concentration. The onset critical temperature and zero resistance critical temperature have been decreased, which were further decreased after oxygen annealing.

Active Site Models for the CuA Site of Peptidylglycine α-Hydroxylating Monooxygenase and Dopamine β-Monooxygenase

A mononuclear copper(II) superoxo species has been invoked as the key reactive intermediate in aliphatic substrate hydroxylation by copper monooxygenases such as peptidylglycine α-hydroxylating monooxygenase (PHM), dopamine β-monooxygenase (DβM), and tyramine β-monooxygenase (TβM). We have recently developed a mononuclear copper(II) end-on superoxo complex using a N-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane tridentate ligand, the structure of which is similar to the four-coordinate distorted tetrahedral geometry of the copper-dioxygen adduct found in the oxy-form of PHM (Prigge, S. T.; Eipper, B. A.; Mains, R. E.; Amzel, L. M. Science2004, 304, 864-867). In this study, structures and physicochemical properties as well as reactivity of the copper(I) and copper(II) complexes supported by a series of tridentate ligands having the same N-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane framework have been examined in detail to shed light on the chemistry dictated in the active sites of mononuclear copper monooxygenases. The ligand exhibits unique feature to stabilize the copper(I) complexes in a T-shape geometry and the copper(II) complexes in a distorted tetrahedral geometry. Low temperature oxygenation of the copper(I) complexes generated the mononuclear copper(II) end-on superoxo complexes, the structure and spin state of which have been further characterized by density functional theory (DFT) calculations. Detailed kinetic analysis on the O(2)-adduct formation reaction gave the kinetic and thermodynamic parameters providing mechanistic insights into the association and dissociation processes of O(2) to the copper complexes. The copper(II) end-on superoxo complex thus generated gradually decomposed to induce aliphatic ligand hydroxylation. Kinetic and DFT studies on the decomposition reaction have suggested that C-H bond abstraction occurs unimolecularly from the superoxo complex with subsequent rebound of the copper hydroperoxo species to generate the oxygenated product. The present results have indicated that a superoxo species having a four-coordinate distorted tetrahedral geometry could be reactive enough to induce the direct C-H bond activation of aliphatic substrates in the enzymatic systems.