Magnetic resonance of the weak organic magnet TDAE-C60

The charge transfer compound TDAE-C₆₀ (TDAE — tetrakis-dimethylamino-ethylene) is so far the only known C₆₀ based molecular ferromagnet. The ESR spectra of TDAE-C₆₀ single crystals demonstrate that freshly grown regularly shaped single crystals show at first an AFM (antiferromagnetic)-like behavior which changes upon annealing at room temperature in vacuum to a FM (ferromagnetic) one. It thus seems that annealing induces a change in the relative orientation of the distorted C ₆₀ ^? ions resulting in a change in the sign of the effective magnetic interactions between neighboring C ₆₀ ^? ions. A structural transition in the TDAE methyl protons at 250 K seems to be connected with this process. Here we review the structure, the ESR spectra, the proton NMR spectra and the¹³C NMR spectra of TDAE-C₆₀.     

Magnetic properties of alkali-intercalated C60 compounds probed by electron spin resonance

In this paper, we present a survey of our ESR results on alkali-intercalated C₆₀ compounds. As we are far from fully understanding the physical properties of fullerides, this article deals successively with the different phases in the phase diagram of A₁C₆₀ compounds. It focuses on both conducting and magnetic properties in metallic compounds, the spin ground state in insulating systems and phase transitions in A₁C₆₀ phases.     

Modeling of metamagnetism in metallic-based materials with first-order transitions

During the past decade, the magnetic properties of metallic-based materials with first-order transitions have been extensively studied, motivated in part by the observation of large magnetocaloric effect (MCE) peaks displayed by these materials near room temperature. These large peaks are believed to be the result of the materials' magnetic properties at the metamagnetic region, characterized by (i) the thermal-induced transition from the ferromagnetic state (FM) to the paramagnetic state (PM) near the Curie temperature (T_C) and (ii) the field-induced transition from PM state to FM state above T_C. We developed a phenomenological model that utilizes the materials' mixed-state probability function to model the materials' complex hysteretic and properties at metamagnetic region. The approximate probability functions are obtained from the first and second derivatives of the magnetization curve. The probability functions are used to separate the materials' magnetization into a FM state component and a PM state component. The applicability of the model is demonstrated for a metallic-based metamagnetic material, Gd₅Si₂Ge₂ compound, where the modeled behaviors show remarkable agreement with the experimental data at the metamagnetic region and provide new physical insights in this mixed-state region. Specifically, in the region of metamagnetic transition, the PM state component is non-reversible and is a function of the FM state component.     

Spin-dependent rectification in the C 59 N molecule

Coherent spin-dependent electron transport is investigated in three conditions: (1) a C₆₀ molecule is connected to two ferromagnetic (FM) electrodes symmetrically, (2) a C₅₉N molecule is connected to two FM electrodes symmetrically and (3) a C₅₉N molecule is connected to two FM electrodes asymmetrically. This work is based on a single-band tight-binding model Hamiltonian and the Green’s function approach with the Landauer–Buttiker formalism. Electrodes used in this study are semi-infinite FM electrodes with finite cross-section. Obvious rectification effect is observed in the C₅₉N molecule which is connected to the FMelectrodes asymmetrically. This effect is more in the P alignment of FM electrodes than in AP alignment of FM electrodes. This study indicates that the rectification behaviour is due to the asymmetry in molecule and junctions. Also in this investigation tunnel magnetoresistance (TMR) is calculated for these molecules. Asymmetry is observed in TMR of C₅₉N which is coupled to the electrodes asymmetrically due to asymmetric junctions, but TMR of C₆₀ is symmetric.     

Study of the effect of Mn and Cu in Fe–Mn–Al–C–Cu alloys by ICEMS and XRD

Experimental analysis of magnetic and structural properties of Fe–Mn–Al–C–Cu alloys with compositions Fe _x Mn_0.915???x Al_0.075C_0.01 (series A) and Fe _x Mn_0.912???x Al_0.075C_0.01Cu_0.003 (series B), 0.500?≤?x?≤?0.800, in steps of 0.050 is presented and discussed. The analysis was performed by integral conversion electrons Mössbauer spectrometry and X-ray diffraction at room temperature. The results suggest, for both series of alloys, that for the highest Mn content, samples exhibit an antiferromagnetic behavior, typical of the FCC or austenite FeMn phase rich in Mn; for those of low Mn content, the coexistence of paramagnetic austenite, typical of the FeMn alloy poor in Mn, a ferromagnetic BCC or ferrite phases can be observed, while for the lowest Mn content, only ferromagnetic (FM) phase tends to prevail. The FM phase is associated to the BCC FeMnAl as was corroborated by X-ray diffraction. The samples with the highest Mn content, the influence of Cu addition is to reduce the mean hyperfine field and to stabilize the antiferromagnetic behavior.     

Intrinsic magnetic inhomogeneity of Eu substituted La0.7Pb0.3Mno3 single crystals

The study of magnetic and magnetotransport properties of the crystals of (La_1−yEu_y)_0.7Pb_0.3MnO₃ system has been carried out. Eu ions enter the crystals being in trivalent nonmagnetic state. Europium ions possessing of smaller ionic radius in comparison with La ions, induce local distortions of Mn–O–Mn bonds in the system that cause random distribution of magnetic exchange interactions in magnitude and, probably, in sign. The competition of magnetic interactions leads to the appearance of the inhomogeneous magnetic state in the crystals. The enhancement of concentration of Eu ions results in decrease of the Curie temperature and broadening of the inhomogeneous magnetic state area. At y=0–0.4 the coexistence of the paramagnetic phase with conductivity of the polaronic type and the ferromagnetic metallic phase is observed in a bounded temperature interval both above and below T_C. Below T_C the increasing of y up to 0.6 induces the magnetic state representing the coexistence of two different FM phases. These phases are spatially separated due to frustration of FM and AFM exchange interactions on phase boundaries. Above T_C, up to 1.6T_C ferromagnetic clusters exist in a paramagnetic matrix similar to the case of samples with y=0–0.4. Concerning electric properties, the samples with y=0–0.4 reveal the metal–insulator transition at temperature that practically coincides with T_C. The sample with y=0.6 has conductivity of insulator character up to the lowest temperatures. For all investigated compositions y=0–0.6 the CMR effect is observed in the area where the inhomogeneous magnetic state exists. The effect is determined by different conductivity of the coexisting phases, as well as by sensitivity of the inhomogeneous state to external magnetic field.     

First-principles studies of magnetic properties and electronic structure of EuC60

The full potential linearized augmented plane wave (FP-LAPW) method with the GGA+U approach was applied to study the electronic structures of the compound Eu₆C₆₀. Present calculations show that the hybridization between the Eu s, d state and the C₆₀ π states plays an essential role in its FM exchange interactions between the 4f electrons and metallic properties.     

Second-order phase transition with coexistence of short-range and long-range ferromagnetic interactions in Ba1.7La0.3FeMoO6 compound

In this work, the magnetic properties and critical behavior around ferromagnetic–paramagnetic (FM–PM) phase transition in Ba_1.7La_0.3FeMoO₆ compound have been investigated in detail. This compound exhibits a second-order magnetic phase transition with Curie temperature T_C = 345 K. The critical exponents β, γ, and δ that are determined by using the modified Arrott plots (MAP), the Kouvel–Fisher (KF) and the critical isotherm analysis agree very well. Our results indicate a coexistence of short-range and long-range ferromagnetic (FM) interactions in Ba_1.7La_0.3FeMoO₆ compound. The existence of long-range FM interactions in this compound can be associated with the crystal structure of materials with long-range Fe/Mo ordering parameter and strength of double-exchange interaction, whereas the existence of the short-range FM interactions can be explained by magnetic inhomogeneity and FM clusters.     

Magnetic phase transitions of antiperovskite Mn3−xFexSnC (0.5≤x≤1.3)

The magnetization and electrical resistivity of Mn_3−xFe_xSnC (0.5≤x≤1.3) were measured to investigate the behavior of the complicated magnetic phase transitions and electronic transport properties from 5 to 300 K. The results obtained demonstrate that Fe doping at the Mn sites of Mn₃SnC induces a more complicated magnetic phase transition than that in its parent phase Mn₃SnC from a paramagnetic (PM) state to a ferrimagnetic (FI) state consisting of antiferromagnetic (AFM) and ferromagnetic (FM) components, while, with the change of Fe-doped content and magnetic field, there is a competition between the AFM component and FM component in the FI state. Both the Curie temperature (T_C) and the saturated magnetization M_s increase with increasing x. The FM component region becomes broader with further increasing Fe-doped content x. The external magnetic field easily creates a saturated FM state (and increased T_C) when . Fe doping quenches the negative thermal expansion (NTE) behavior from 200 to 250 K reported in Mn₃SnC.     

Magnetism of C60-based molecular complexes: High-field-magnetization and magnetooptical study

Magnetization study of the C₆₀ · TMTSF · 2CS₂ molecular complex in magnetic fields up to 47 T for the temperature range 1.8–300 K and ESR spectroscopy of the molecular complex (ET)₂C₆₀ at T=1.8 K for the frequency range 60–90 GHz in magnetic fields up to 32 T provide experimental evidence that paramagnetic centers with reduced g-factor values g<1 control the magnetic properties of these solids. A model is suggested in which the renormalization of the g factor is due to the dynamic Jahn-Teller effect involving negative C₆₀ ions that appear as defects in the crystalline structure with a weak charge transfer.     

Sign reversal of the magnetoplastic effect in C60 single crystals during the sc-fcc phase transition

It is found that the magnetoplastic effect in C₆₀ single crystals in a pulsed magnetic field with induction larger than 10 T changes its sign in the vicinity of the phase transition at T _c =250–260 K: crystal strengthening is observed for T<T _c , and softening occurs for T>T _c . This indicates a change in the crystal lattice structure in the magnetic field.     

The electronic and magnetic properties of （Mn,C）-codoped ZnO diluted magnetic semiconductor

The electronic and magnetic properties of (Mn,C)-codoped ZnO are studied in the Perdew-Burke-Ernzerhof form of generalized gradient approximation of the density functional theory. By investigating five geometrical configurations, we find that Mn doped ZnO exhibits anti-ferromagnetic or spin-glass behaviour, and there are no carriers to mediate the long range ferromagnetic (FM) interaction without acceptor co-doping. We observe that the FM interaction for (Mn,C)-codoped ZnO is due to the hybridization between C 2p and Mn 3d states, which is strong enough to lead to hole-mediated ferromagnetism at room temperature. Meanwhile, we demonstrate that ZnO co-doped with Mn and C has a stable FM ground state and show that the (Mn,C)-codoped ZnO is FM semiconductor with super-high Curie temperature (T C = 5475 K). These results are conducive to the design of dilute magnetic semiconductors with codopants for spintronics applications.     

Complete pentagon orientational ordering in C60 fullerite charged with NO

Solid C₆₀ was stored in NO under high pressure, and the gas molecules NO were found to diffuse into the octahedral interstitial sites in its fcc crystal lattice. Its ¹³C NMR MAS spectra are composed of a primary resonance at 143.7 ppm accompanied by two minor peaks shifted 0.4 and 0.8 ppm downfield, respectively. The dopant was found to depress its phase transition temperature at 260 K in pure C₆₀ and to substantially reduce the drop Δ?′ at the phase transition temperature. Furthermore, the spectral features associated with relaxation during glass transition at lower temperature, as observed in impedance spectra, were smeared. The fraction of P-orientation below T _c was calculated to be larger than 11/12. These results show that a completely P-oriented phase occurred in (NO)_0.1C₆₀ and that this phase is favored by a negative pressure on the C₆₀ lattice exerted by NO, as well as by the electrostatic interaction between the two.     

Effects of divalent alkaline earth ions on the magnetic and transport features of La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) compounds

We have studied the magnetic and transport properties of Fe doped La_0.65A_0.35Mn_0.95Fe_0.05O₃ (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (T_C) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and T_C are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of T_C and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost.     

Effect of Al doping on the magnetic and electrical properties of layered perovskite La1.3Sr1.7Mn2−xAlxO7

The effect of Al substitution for Mn site in layered manganese oxides La_1.3Sr_1.7Mn_2−xAl_xO₇ on the magnetic and electrical properties has been investigated. It is interesting that all the samples undergo a similar and complex transition with lowing temperature; they transform from the two-dimensional short-range ferromagnetic order at T*, then enter the three-dimensional long-range ferromagnetic state at T_C, at last they display the canted antiferromagnetic state below T_N. T*, T_C and T_N are all reduced with Al content. Resistivity increases sharply with increasing Al concentration, and the metal-insulator transition disappears when x reaches 10%. Additionally, magnetoresistance (MR) effect is weakened. Al substitution dilutes the magnetic active Mn-O-Mn network and weakens the double exchange interaction, and further suppresses FM ordering and metallic conduction. Owing to the anisotropic interaction in the layered perovskite, the magnetic and electrical properties are more sensitive to Al doping level than those in ABO₃-type perovskite.     

Structure, electronic and magnetic properties of Cr-doped (ZnS)12 clusters: A first-principles study

We have studied the structural, electronic, and magnetic properties of (ZnS)₁₂ clusters doped with one (monodoped) and two (bidoped) Cr atoms in terms of a first-principles method. Substitutional, exohedral, and endohedral doping are considered. The substitutional isomer is found to be most favorable in energy for monodoped clusters, while the exohedral isomers are found to be most favorable for bidoped clusters. The magnetic coupling between the Cr atoms is mainly governed by the competition between direct Cr-Cr antiferromagnetic (AFM) interaction and the ferromagnetic (FM) interaction between two Cr atoms via S atom due to strong p-d hybridization. Finally, we show that the exohedral bidoped (ZnS)₁₂ clusters favor the FM state, which has potential applications in nanoscale quantum devices.     

Magnetostriction and magnetization measurements on a DyNi2B2C single crystal in a magnetic field

In order to investigate the interactions between lattice properties, magnetic ordering and superconductivity of DyNi₂B₂C, thermal expansion, magnetostriction and magnetization measurements were performed for T=2–15 K and for μ₀H=0–3 T on a single crystal in the crystallographic [1 1 0] direction. A magnetic phase diagram is derived that shows two phases (AF1 and AF2) in the narrow region between the zero-field antiferromagnetic AF and the induced ferromagnetic state FM. Moreover, it is characterized by a large-field hysteresis. This behaviour can be described by a two domain magnetic state. The metamagnetic structure AF1 with about a quarter of the saturated magnetization is responsible for suppressing the superconductivity in DyNi₂B₂C because of its ferromagnetic component.     

Radiation-stimulated modification of C60 films on Si-oxide surfaces

The electronic structure of C₆₀/SiO_x/Si(1 0 0) interface was studied by photoemission (valence-bands, C 1s, and Si 2p core levels) and near-edge X-ray absorption fine structure (C 1s threshold) spectroscopies. It was concluded that the SiO_x/Si surface is non-reactive with respect to the interaction with C₆₀. The exposure of the C₆₀/SiO_x/Si system under non-monochromatic synchrotron radiation causes modification of the electronic structure of this system. It is explained by polymerization of the C₆₀ molecules and arising a strong ionic-like interaction of the polymerized C₆₀ with the SiO_x surface. Annealing of this system up to temperatures of 550–625 °C leads to complete desorption of the C₆₀ molecules from the non-irradiated sample areas while the modified by radiation fullerenes remain attached to the substrate.     

Mechanisms of inelastic scattering of low-energy protons by C6H6, C60, C6F12, and C60F48 molecules

The mechanisms of inelastic scattering of low-energy protons with a kinetic energy of 2–7 eV by C₆H₆, C₆F₁₂, C₆₀, and C₆₀F₄₈ molecules are studied using the methods of quantum chemistry and nonempirical molecular dynamics. It is shown that, for the C₆H₆ + proton and C₆₀ + proton systems, starting from a distance of 6 Å from the carbon skeleton, the electronic charge transfer from the aromatic molecule to H⁺ occurs with a probability close to unity and transforms the H⁺ ion into a hydrogen atom and the neutral C₆H₆ and C₆₀ molecules into cation radicals. The mechanism of interaction of low-energy protons with C₆F₁₂ and C₆₀F₄₈ molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the noncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized, on the one hand, on the positively charged hydrogen ion and, on the other hand, on the C₆F₁₂ and C₆₀F₄₈ molecules. As a result, the neutral molecule + proton state becomes the ground state. In turn, this inversion makes the electronic charge transfer energetically unfavorable. Quantum-chemical and molecular-dynamics calculations on different levels of theory showed that, for fluorine derivatives of some aromatic structures (C₆F₁₂, C₆₀F₄₈), the barriers to proton penetration through carbon hexagons are two to four times lower than for the corresponding parent systems (C₆H₆, C₆₀). This effect is explained by the absence of active π-electrons in the case of fluorinated molecules.