Jahn-Teller Centers Research Articles

Electrochemical Storage Behavior of a High-Capacity Mg-Doped P2-Type Na2/3Fe1-yMnyO2 Cathode Material Synthesized by a Sol-Gel Method.

Grid-scale energy storage applications can benefit from rechargeable sodium-ion batteries. As a potential material for making non-cobalt, nickel-free, cost-effective cathodes, earth-abundant Na2/3Fe1/2Mn1/2O2 is of particular interest. However, Mn3+ ions are particularly susceptible to the Jahn-Teller effect, which can lead to an unstable structure and continuous capacity degradation. Modifying the crystal structure by aliovalent doping is considered an effective strategy to alleviate the Jahn-Teller effect. Using a sol-gel synthesis route followed by heat treatment, we succeeded in preparing an Mg-doped Na2/3Fe1-yMnyO2 cathode. Its electrochemical properties and charge compensation mechanism were then studied using synchrotron-based X-ray absorption spectroscopy and in situ X-ray diffraction techniques. The results revealed that Mg doping reduced the number of Mn3+ Jahn-Teller centers and alleviated high voltage phase transition. However, Mg doping was unable to suppress the P2-P'2 phase transition at a low voltage discharge. An initial discharge capacity of about 196 mAh g-1 was obtained at a current density of 20 mAh g-1, and 60% of rate capability was maintained at a current density of 200 mAh g-1 in a voltage range of 1.5-4.3 V. This study will greatly contribute to the ongoing search for advanced and efficient cathodes from earth-abundant elements for rechargeable sodium-ion batteries operable at room temperature.

Magnetocaloric properties of Fe-substituted La–Sr-manganites

The effect of Fe doping on the structural, magnetic and magnetocaloric properties was studied on La1-xSrxMn1-yFeyO3 (x = 0.10, 0.20; y = 0.00, 0.10, 0.15) manganites prepared by solid state reaction method. X-ray structural analysis showed that the substitution of manganese by iron does not change the phase state in the rhombohedral series (x = 0.20). In the orthorhombic series (x = 0.1), the substitution of manganese by iron leads to a phase transition from the Jahn-Teller O′ phase to the ordinary O phase. We explain this transition by a decrease in the concentration of Mn3+ ions, which are Jahn-Teller centers. In addition, we recorded an increase in the unit cell parameters in the iron-containing samples of both series. We explain this effect by the presence of a certain amount of Fe4+ ions. Magnetic measurements showed that all samples undergo a second order FM–PM transition at the Curie temperature (Tc). The Curie temperature TC and the Curie-Weiss temperature (Θ) decrease with increasing Fe content. The relationship between the variation of TC and structural parameters the Me–O bond length and the bond angle of Me–O–Me with increasing Fe content has been established. In the paramagnetic temperature range, the formation of magnetic clusters was suggested from isothermal magnetization data. For a magnetic field variation of 5 T, the entropy change is evaluated.

Light induced electron spin resonance properties of van der Waals CrX3 (X = Cl, I) crystals

The research on layered van der Waals (vdW) magnets is rapidly progressing owing to exciting fundamental science and potential applications. In bulk crystal form, CrCl3 is a vdW antiferromagnet with in-plane ferromagnetic ordering below 17 K, and CrI3 is a vdW ferromagnet below 61 K. Here, we report on the electron spin resonance (ESR) properties of CrCl3 and CrI3 single crystals upon photo-excitation in the visible range. We noticed remarkable changes in the ESR spectra upon illumination. In the case of CrCl3, at 10 K, the ESR signal is shifted from g = 1.492 (dark) to 1.661 (light), the linewidth increased from 376 to 506 Oe, and the signal intensity is reduced by 1.5 times. Most interestingly, the observed change in the signal intensity is reversible when the light is cycled on/off. We observed almost no change in the ESR spectral parameters in the paramagnetic phase (>20 K) upon illumination. Upon photo-excitation of CrI3, the ESR signal intensity is reduced by 1.9 times; the g-value increased from 1.956 to 1.990; the linewidth increased from 1170 to 1260 Oe at 60 K. These findings are discussed by taking into account the skin depth, the slow relaxation mechanism, and the appearance of low-symmetry fields at the photo-generated Cr2+ Jahn–Teller centers. Such an increase in the g-value as a result of photo-generated Cr2+ ions is further supported by our many-body wavefunction calculations. This work has the potential to extend to monolayer vdWs magnets by combining ESR spectroscopy with optical excitation and detection.

Sub-lattice of Jahn-Teller centers in hexaferrite crystal

A novel type of sub-lattice of the Jahn-Teller (JT) centers was arranged in Ti-doped barium hexaferrite BaFe12O19. In the un-doped crystal all iron ions, sitting in five different crystallographic positions, are Fe3+ in the high-spin configuration (S = 5/2) and have a non-degenerate ground state. We show that the electron-donor Ti substitution converts the ions to Fe2+ predominantly in tetrahedral coordination, resulting in doubly-degenerate states subject to the Eotimes e problem of the JT effect. The arranged JT complexes, Fe2+O4, their adiabatic potential energy, non-linear and quantum dynamics, have been studied by means of ultrasound and terahertz-infrared spectroscopies. The JT complexes are sensitive to external stress and applied magnetic field. For that reason, the properties of the doped crystal can be controlled by the amount and state of the JT complexes.

Highly-stable P2–Na0.67MnO2 electrode enabled by lattice tailoring and surface engineering

One of the key challenges of sodium ion batteries is to develop sustainable, low-cost and high capacity cathodes, and this is the reason that layered sodium manganese oxides have attracted so much attention. However, the undesired phase transitions and poor electrolyte-electrode interfacial stability facilitate their capacity decay and limit their practical applications. Herein, we design a novel Al2O3@Na0.67Zn0.1Mn0.9O2 electrode to mitigate these problems, by taking the advantages of both structural stabilization and surface passivation via Zn2+ substitution and Al2O3 atomic layered deposition (ALD) coating, respectively. Long-range and local structural analyses during charging/discharging processes indicate that P2–P2’ phase transformation can be suppressed by substituting proper amount of Mn3+ Jahn-Teller centers with Zn2+, whereas excessive Zn2+ leads to P2-OP4 structure transition at low sodium contents and facilitates the electrode degradations. Furthermore, the homogeneous and robust cathode electrolyte interphase (CEI) layers formed on the Al2O3-coated electrodes effectively hinder the organic electrolytes from further decomposition. Therefore, our synergetic strategy of Zn2+ substitution and ALD surface engineering remarkably boosts the cycling performance of P2–Na0.67MnO2 and provides some new insights into the designing of highly stable cathode electrodes for sustainable sodium ion batteries.

Acoustic Properties of Crystals with Jahn–Teller Impurities: Elastic Moduli and Relaxation Time. Application to SrF2:Cr2+

A new approach to evaluate the relaxation contribution to the total elastic moduli for crystals with Jahn–Teller (JT) impurities is worked out and applied to the analysis of the experimentally measured ultrasound velocity and attenuation in SrF2:Cr2+. Distinguished from previous work, the background adiabatic contribution to the moduli, important for revealing the impurity relaxation contribution, is taken into account. The temperature dependence of the relaxation time for transitions between the equivalent configurations of the JT centers has been obtained, and the activation energy for the latter in SrF2:Cr2+, as well as the linear vibronic coupling constant have been evaluated.

The Jahn-Teller and pseudo Jahn-Teller effect in materials science

Defining materials science as a translation from microscopic foundations of matter to macroscopic performance in applications, this mostly review paper is devoted to the special features of matter with Jahn-Teller (JT) and pseudo JT (PJT) centers that makes it outstanding in the search of novel properties and applications as novel materials. There are three kinds of problems in this respect. The first is related to the difficulties in the use of computer simulation of observable properties (a methodology widely employed in materials science) in application to systems with dynamic JT and PJT effects. The second is due to the specifics of such systems in interaction with external perturbations, which contribute with a strong orientational effect that enhances the observable properties by orders of magnitude. The third kind of problems relevant to materials science is in the use of the JT and PJT effects in revealing the origin of structural properties of a relevant polyatomic system and working out methods to influence them in designing novel materials.The paper formulates these problems and provides for examples that demonstrate their importance. For the second group of problems, illustrative examples include flexoelectricity, permittivity, and electrostriction in systems with dynamical JT and PJT centers, and it is shown that the latter enhance the observable properties by several orders of magnitude. Also related to this group of problems are the magnetic-dielectric bistabilities in molecular systems and solids induced by JT and PJT effect, illustrated on molecules like CuF3 and crystals of the type LiCuO2. The third group of problems is shown by the already multiply used application of the PJTE to reveal the origin of distortions of planar configuration in 2D (graphene-like) and quasi-2D materials and to work out methods of restoration of their planar configurations by means of external perturbations.

Cooperative Jahn–Teller phase transition of icosahedral molecular units

Non-linear molecules undergo distortions when the orbital degeneracy of the highest occupied level is lifted by the Jahn–Teller effect. If such molecules or clusters of atoms are coupled to one another, the system may experience a cooperative Jahn–Teller effect (CJTE). In this paper, we describe a model of how the CJTE leads to the crystallization of the disordered phase. The model Hamiltonian is based on a normal mode decomposition of the clusters in order to maintain the symmetry labels. We take account of the electron-strain and the electron-phonon couplings and, by displacing the coordinates of the oscillators, obtain a term that explicitly couples the Jahn–Teller centers, enabling us to perform a mean-field analysis. The calculation of the free energy then becomes straightforward, and obtaining phase diagrams in various regimes follows from the minimization of this free energy. The results show that the character of the phase transition may change from strong to weak first order and even to second-order, depending on the coupling to the vibrational modes. Taken together, these results may serve as a paradigm for crystallization near the transition temperature, where the atoms tend to form clusters of icosahedral symmetry.

Optical evidence of quantum rotor orbital excitations in orthorhombic manganites

In magnetic compounds with Jahn–Teller (JT) ions (such as Mn3+ or Cu2+), the ordering of the electron or hole orbitals is associated with cooperative lattice distortions. There the role of JT effect, although widely recognized, is still elusive in the ground state properties. Here we discovered that, in these materials, there exist excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantized as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO3 using ellipsometry technique. They appear clearly as narrow sidebands accompanying the electron transition between the JT split orbitals at neighboring Mn3+ ions, displaying anomalous temperature behavior around the Néel temperature T N ≈ 140 K. We present these results together with new experimental data on photoluminescence found in LaMnO3, which lend additional support to the ellipsometry implying the electronic-vibrational origin of the quantum rotor orbital excitations. We note that the discovered orbital excitations of quantum rotors may play an important role in many unusual properties observed in these materials upon doping, such as high-temperature superconductivity and colossal magnetoresistance.

Magnetic Field Induced Relaxation Attenuation of Ultrasound by Jahn–Teller Centers: Application to ZnSe:Cr2+

The influence of magnetic fields on ultrasonic attenuation caused by relaxation in Jahn–Teller centers is studied using chromium ions as Zn substitute impurities in the ZnSe crystal as an example. The changes of the position and shape of the relaxation peak with the applied magnetic field induction B were observed in the temperature dependence of the ultrasonic attenuation of the shear waves at the frequency of 29.5 MHz propagating along the [110] axis with the polarization vector parallel to the [1\(\overline{1}\)0] axis. To rationalize the results, a simulation procedure was employed assuming that there are two thermal activation mechanism of relaxation with different relaxation times. One of them emerged with activation energy \(V_0=75\) K that remains unchanged in the magnetic fields, the other occurs with increasing \(V_0\) up to \(V_0=106\) K at \(B=14\) T.

Vibronic interaction in crystals with the Jahn-Teller centers in the elementary energy bands concept

The order-disorder type phase transition caused by the vibronic interaction (collective Jahn-Teller effect) in a monoclinic CuInP$_2$S$_6$ crystal is analyzed. For this purpose, a trigonal protostructure model of CuInP$_2$S$_6$ is created, through a slight change in the crystal lattice parameters of the CuInP$_2$S$_6$ paraelectric phase. In parallel to the group-theoretical analysis, the DFT-based {\it ab initio} band structure calculations of the CuInP$_2$S$_6$ protostructure, para-, and ferriphases are performed. Using the elementary energy bands concept, a part of the band structure from the vicinity of the forbidden energy gap, which is created by the $d$-electron states of copper, has been related with a certain Wyckoff position where the Jahn-Teller's centers are localized. A construction procedure of the vibronic potential energy matrix is generalized for the case of crystal using the elementary energy bands concept and the group theoretical method of invariants. The procedure is illustrated by the creation of the adiabatic potentials of the $\Gamma_5$-$\Gamma_5$ vibronic coupling for the protostructure and paraphase of the CuInP$_2$S$_6$ crystal. A structure of the obtained adiabatic potentials is analyzed, followed by conclusions on their transformation under a phase transition and the discussion on the possibility for the spontaneous polarization to arise in this crystal.

Relaxation Attenuation of Ultrasound by the Jahn-Teller Centers in ZnSe:Cr in High Magnetic Fields

The magnetic field dependence of ultrasonic attenuation α (B) of slow shear waves in the ZnSe:Cr2+crystal at a number of fixed temperatures fromT=1.4 K to 20 K in magnetic fields of up toB=14 T were investigated. For magnetic fieldsBabove 5 T we found that the attenuation increases with B monotonically, and at a given temperature it is proportional to the magnitude of relaxation attenuation atB=0. We show that the magnetic field dependent attenuation is due to the change in populations of the lowest energy levels of the impurity centers CrZn4Se, produced by the Jahn-Teller effect and split by the spin-orbital interaction and the magnetic field. The calculations carried out without fitting parameters are in good agreement with the experimental data.

Percolation features of cooperative Jahn-Teller systems: Ising EFT framework

Elastic exchange between two nearest Jahn-Teller (JT) centers in two or three dimensional dense crystals, can give an ordered macroscopic distortion known as cooperative JT effect (CJTE). A very diluted JT crystal does not show this effect. In the dynamic JT effect (DJTE), tunneling between different equivalent distorted wells has a pronounced influence on the CJTE. We investigate this phenomenon using a progressive increase in the concentration of these centers in the JT crystals, based on a bond percolation vector spin analogy technique within the framework of effective field theory (EFT). Mean field theory (MFT) was extensively used in previous studies of CJTE; however it neither includes correlation between JT centers in the lattice due to the complexity of the distortion field in the crystal nor the effect of tunneling between wells. We resort to an alternative procedure, by describing a JT center as a pseudo-spin vector $$\vec S$$ , induced to represent the degenerate JT-distorted states, where two nearest JT centers interact via an elastic exchange described by an Ising type spin interaction. The DJTE is considered to be similar to an elastic transverse field term in the Hamiltonian portraying the effect of tunneling between equivalent wells in the adiabatic potential energy surface (APES). We will be particularly discussing S = 1, S = 3/2 and S = 5/2 spin cases, where 2S + 1 wells in the APES are present and what JT systems they actually represent, with a percolative mechanism applied to the interactions between different JT centers. The different lattices are distinguished by their coordination numbers. Strong tunneling effects can suppress the CJTE and lead to a new state of criticality. Generalizations to higher spin systems will be obtained using a scaling technique. For the relevant distortions, we determine single site correlations, the macroscopic average distortion describing a structural phase transition and the elastic isothermal susceptibility as a function of temperature. The critical bond percolation threshold and the critical tunneling parameter are also obtained.

Ultrasonic exploration of vacancy centres with the Jahn-Teller effect. Application to the ZnSe crystal

We show that the structure, properties, and concentration of vacancies in crystals can be studied by ultrasonic experiments previously employed for impurity centres only. Measurements of the temperature dependence of attenuation and phase velocities of ultrasonic shear waves of 52 MHz propagating along the crystallographic axis [110] of nominally pure ZnSe single crystals (grown by the seeded physical vapour transport method) show strong anomalies which are typical for relaxation processes in system with isolated Jahn–Teller (JT) centres. The observed JT distortion mode is trigonal, subject to a threefold orbitally degenerate T-term interaction with trigonal and tetragonal nuclear displacements. In the absence of sufficiently high concentrations of impurity atoms with such properties we attributed the observed JT centres to zinc vacancies. The temperature dependence of the isothermal and adiabatic forms of the appropriate elastic modulus and the relaxation time show that the relaxation mechanism changes from thermal activation at higher temperatures to tunnelling through a potential energy barrier below 18 K. We provide an estimate of the magnitude of the potential barrier, as well as the pseudorotation frequency and concentration of vacancies. Also we determine the extremum points of the adiabatic potential energy surface of the vacancy centre.

Direct visualization of the Jahn-Teller effect coupled to Na ordering in Na5/8MnO2.

The cooperative Jahn-Teller effect (CJTE) refers to the correlation of distortions arising from individual Jahn-Teller centres in complex compounds. The effect usually induces strong coupling between the static or dynamic charge, orbital and magnetic ordering, which has been related to many important phenomena such as colossal magnetoresistance and superconductivity. Here we report a Na5/8MnO2 superstructure with a pronounced static CJTE that is coupled to an unusual Na vacancy ordering. We visualize this coupled distortion and Na ordering down to the atomic scale. The Mn planes are periodically distorted by a charge modulation on the Mn stripes, which in turn drives an unusually large displacement of some Na ions through long-ranged Na-O-Mn(3+)-O-Na interactions into a highly distorted octahedral site. At lower temperatures, magnetic order appears, in which Mn atomic stripes with different magnetic couplings are interwoven with each other. Our work demonstrates the strong interaction between alkali ordering, displacement, and electronic and magnetic structure, and underlines the important role that structural details play in determining electronic behaviour.

Electronic structure ofBa3CuSb2O9: A candidate quantum spin liquid compound

Using density-functional methods, we study the electronic structure of ${\mathrm{Ba}}_{3}\mathrm{Cu}{\mathrm{Sb}}_{2}{\mathrm{O}}_{9}$, a candidate material for the quantum spin liquid behavior. We study both the triangular lattice as well as the recently proposed hexagonal lattice structures with flipped Cu-Sb dumbbells. The band structure near the Fermi energy is described very well by a tight-binding Hamiltonian involving the Cu (${e}_{g}$) orbitals, confirming their central role in the physics of the problem. A minimal tight-binding Hamiltonian for the triangular structure is presented. The Cu (${d}^{9}$) ions (a single ${e}_{g}$ hole in the band structure) present in the compound are expected to be Jahn-Teller centers, while the nature of the Jahn-Teller distortions in this material is still under debate. Solving a simple model by exact diagonalization, we show that electronic correlation effects in general enhance the tendency towards a Jahn-Teller distortion by reducing the kinetic energy due to correlation effects. Our density-functional calculations do indeed show a significant Jahn-Teller distortion of the $\mathrm{Cu}{\mathrm{O}}_{6}$ octahedra when we include the correlation effects within the Coulomb-corrected GGA+U method, so that the Jahn-Teller effect is correlation driven. We argue for the presence of a random static Jahn-Teller distortion in the hexagonal structure rather than a dynamical one because of the broken octahedral symmetry around the $\mathrm{Cu}{\mathrm{O}}_{6}$ octahedra and the potential fluctuations inherently present in the system caused by a significant disorder, which is believed to be present, in particular, due to the flipped Cu-Sb dumbbells.

Vibronic excitation dynamics in orbitally degenerate correlated electron system

Orbital-lattice coupled excitation dynamics in orbitally degenerate correlated systems are examined. We present a theoretical framework, where both local vibronic excitations and superexchange-type inter-site interactions are dealt with on an equal footing. We generalize the spin-wave approximation so as to take local vibronic states into account. Present method is valid from weak to strong Jahn-Teller coupling magnitudes. Two characteristic excitation modes coexist; a low-energy dispersive mode and high-energy multi-peak mode. These are identified as a collective vibronic mode, and Flanck-Condon excitations in a single Jahn-Teller center modified by the inter-site interactions, respectively. Present formalism covers vibronic dynamics in several orbital-lattice coupled systems.

Ion channeling study of lattice distortions in chromium-doped SrTiO3 crystals

The results of ion channeling studies of lattice distortions in SrTiO3: Cr single crystals are presented. Two types of single crystals containing the same amount of Cr impurities but differing in stoichiometry have been investigated. The single crystals grown by the Verneuil method have the compositions of standard-grown SrTiO3: Cr (0.05 at % Cr), whereas the single crystals grown with a strontium deficiency and a chromium compensating amount have the composition Sr0.9995TiO3 (0.05 at % Cr). Analysis of the angular channeling spectra indicates that, in crystals of both types, the main defects are Cr impurities located in octahedral sites. In the SrTiO3: Cr crystals, impurity atoms manifest themselves as Cr4+ with tetragonal Jahn-Teller distortions of the surrounding lattice. In the Sr0.9995TiO3: Cr crystals grown with a Sr deficiency, the characteristic displacements of Ti ions in the third coordination sphere of the Jahn-Teller center Cr4+ exhibit the effect of interaction of the center with a neighboring vacancy in the Sr sublattice.

Relaxation and resonance ultrasound attenuation by Jahn-Teller centers in a GaAs:Cu crystal

The interaction of ultrasound with CuGa4As in a GaAs:Cu crystal has been experimentally studied. The temperature dependences of the attenuation of all normal ultrasonic modes propagating in the 〈110〉 direction both in doped copper and in nominally pure gallium arsenide crystals have been measured. In the GaAs:Cu crystal, the attenuation peak has been revealed for a transverse wave polarized along the 〈110〉 axis whose elastic shifts correspond to the symmetry of the tetragonal mode of the Jahn-Teller effect. The temperature dependence of the attenuation of this wave indicates that two types of attenuation—relaxation and resonance—occur. The constructed temperature dependence of the relaxation time indicates that tunneling through the potential barrier between the minima of the adiabatic potential energy is the main relaxation mechanism at temperatures below 10 K. Tunneling splitting estimated from experimental data is in good agreement with the theoretical estimate.

Nuclear tunneling and dynamical Jahn-Teller effect in graphene with vacancy

We show that the substitutional vacancy in graphene forms a dynamical Jahn-Teller center. The adiabatic potential surface resulting from the electron-lattice coupling was computed using density-functional methods and subsequently the Schr\"odinger equation was solved for the nuclear motion. Our calculations show a large tunnelling splitting $3 \Gamma$ of about 86 cm$^{-1}$. %, which is large as compared to the typical strain splitting. The effect results in a large delocalization of the carbon nuclear wave functions around the vacancy leading to a significant broadening of the Jahn-Teller active $sp^2\sigma$ electron states. The tunnelling splitting should be observable in electron paramagnetic resonance and two-photon resonance scattering experiments.