Cyclotron motion in the vicinity of a Lifshitz transition in graphite.

Graphite, a model (semi)metal with trigonally warped bands, is investigated with a magnetoabsorption experiment and viewed as an electronic system in the vicinity of the Lifshitz transition. A characteristic pattern of up to 20 cyclotron resonance harmonics has been observed. This large number of resonances, their relative strengths and characteristic shapes trace the universal properties of the electronic states near a separatrix in momentum space. Quantum-mechanical perturbative methods with respect to the trigonal warping term hardly describe the data which are, on the other hand, fairly well reproduced within a quasiclassical approach and conventional band structure model. Trigonal symmetry is preserved in graphite in contrast to a similar system, bilayer graphene.

Anisotropic long-range spin transport in canted antiferromagnetic orthoferrite YFeO3.

In antiferromagnets, the efficient transport of spin-waves has until now only been observed in the insulating antiferromagnet hematite, where circularly (or a superposition of pairs of linearly) polarized spin-waves diffuse over long distances. Here, we report long-distance spin-transport in the antiferromagnetic orthoferrite YFeO3, where a different transport mechanism is enabled by the combined presence of the Dzyaloshinskii-Moriya interaction and externally applied fields. The magnon decay length is shown to exceed hundreds of nanometers, in line with resonance measurements that highlight the low magnetic damping. We observe a strong anisotropy in the magnon decay lengths that we can attribute to the role of the magnon group velocity in the transport of spin-waves in antiferromagnets. This unique mode of transport identified in YFeO3 opens up the possibility of a large and technologically relevant class of materials, i.e., canted antiferromagnets, for long-distance spin transport.

High-frequency electron paramagnetic resonance analysis of the oxidation state and local structure of Ni and Mn ions in Ni,Mn-codoped LiCoO(2).

High-frequency electron paramagnetic resonance (HF-EPR) spectroscopy was employed to examine the oxidation state and local structure of Ni and Mn ions in Ni,Mn-codoped LiCoO(2). The assignment of EPR signals was based on Mg,Mn-codoped LiCoO(2) and Ni-doped LiCoO(2) used as Mn(4+) and low-spin Ni(3+) EPR references. Complementary information on the oxidation state of transition-metal ions was obtained by solid-state (6,7)Li NMR spectroscopy. For slightly doped oxides (LiCo(1-x)Ni(x)Mn(x)O(2) with x < 0.05), nickel and manganese substitute for cobalt in the CoO(2) layers and are stabilized as Ni(3+) and Mn(4+) ions. The local structure of Mn(4+) ions was determined by modeling of the axial zero-field-splitting parameter in the framework of the Newman superposition model. It has been found that the local trigonal distortion around Mn(4+) is smaller in comparison with that of the host site. To achieve a local compensation of Mn(4+) charge, several defect models are discussed. With an increase in the total dopant content (LiCo(1-x)Ni(x)Mn(x)O(2) and 0.05

Long-distance spin-transport across the Morin phase transition up to room temperature in ultra-low damping single crystals of the antiferromagnet α-Fe2O3.

Antiferromagnetic materials can host spin-waves with polarizations ranging from circular to linear depending on their magnetic anisotropies. Until now, only easy-axis anisotropy antiferromagnets with circularly polarized spin-waves were reported to carry spin-information over long distances of micrometers. In this article, we report long-distance spin-transport in the easy-plane canted antiferromagnetic phase of hematite and at room temperature, where the linearly polarized magnons are not intuitively expected to carry spin. We demonstrate that the spin-transport signal decreases continuously through the easy-axis to easy-plane Morin transition, and persists in the easy-plane phase through current induced pairs of linearly polarized magnons with dephasing lengths in the micrometer range. We explain the long transport distance as a result of the low magnetic damping, which we measure to be ≤ 10-5 as in the best ferromagnets. All of this together demonstrates that long-distance transport can be achieved across a range of anisotropies and temperatures, up to room temperature, highlighting the promising potential of this insulating antiferromagnet for magnon-based devices.

Local coordination of Fe(3+) in layered LiCo(1-y)Al(y)O(2) oxides determined by high-frequency electron paramagnetic resonance spectroscopy.

The local coordination of Fe(3+) spin probes in trigonal LiAl(y)Co(1-y)O(2) was studied using high-frequency electron paramagnetic resonance spectroscopy. This technique allows the determination of Fe(3+) ions in respect to axial and rhombic zero-field splitting parameters (ZFS). After the progressive replacement of Co by Al, the axial D parameter of Fe(3+) increases from +0.0548 to +0.2802 cm(-1). On the same order, the rhombic E parameter decreases. Structural information about the Fe(3+) site in layered LiAl(y)Co(1-y)O(2) oxides was based on modeling of the magnitude of the ZFS parameters by means of the Newman superposition model. It was found that the first metal coordination sphere including Co(3+) and Al(3+) ions gave rise to differentiation of the Fe(3+) dopants in respect to local trigonal and rhombic distortion. The maximum trigonal distortion for the FeO(6) octahedron was achieved when Fe(3+) spin probes were surrounded by Al only, while the Co environment yields a rhombic distortion of the FeO(6) octahedron.

Tuning the magnetic properties of the high-spin molecular cluster Fe8.

The synthesis, crystal structure, and magnetic characterization of a high-spin cluster comprising eight iron ions are presented in this contribution. The cluster has formula [(tacn)6Fe8O2(OH)12Br4.3(ClO4)3.7]·6H2O (Fe8pcl), where tacn is the organic ligand 1,4,7-triazacyclononane. It can be considered a derivative of Fe8 Br8 , a cluster whose low-temperature magnetization dynamics has been extensively investigated, in which four of the bromide ions have been replaced by perchlorate anions. The structure of the central core of the two molecules, [Fe8O(OH)12(tacn)6](8+), is essentially the same, but Fe8pcl has a higher symmetry (the bromide derivative crystallizes in the acentric P1 space group while Fe8pcl crystallizes in the monoclinic P2(1)/c space group). The magnetic properties of Fe8pcl suggest it is very similar to Fe8Br8 having a S=10 ground state as well. The zero-field splitting parameters were accurately determined by high field-high frequency EPR (HF-EPR) measurements. The two clusters have similar axial anisotropy D but Fe8pcl has a larger transverse anisotropy E: The value of E/D is 0.21 for the perchlorate derivative but 0.19 for Fe8Br8. AC susceptibility measurements revealed the cluster behaves like a superparamagnetic particle. However, due to the occurrence of large terms in the transverse anisotropy, the temperature dependence of the relaxation time cannot be reproduced by a simple Arrhenius law model. As observed in the bromide derivative, below 350 mK the relaxation time becomes temperature independent and indicating that a pure tunneling regime is attained. The comparison of the tunneling rate in the two clusters shows that in the perchlorate derivative the relaxation process is 35 times faster. The observed ratio of the tunneling rates is in reasonable agreement with that calculated from the tunneling splitting, namely the energy difference between the two almost-degenerate lowest levels Ms =±10, in the two clusters.

Parity non conservation: NMR parameters in chiral molecules.

The formula giving the parity-violating electroweak interaction contribution to the magnetic shielding tensor has been applied to enantiomers containing thallium. Using an extended Hückel relativistically parameterized method a chemical shift difference close to 1 mHz at 11.7 T is calculated in two couples of enantiomers. Such a difference is slightly lower than the extreme line width which may be actually reached in ultra-high resolution NMR.

How perfect can graphene be?

We have identified the cyclotron resonance response of the purest graphene ever investigated, which can be found in nature on the surface of bulk graphite, in the form of decoupled layers from the substrate material. Probing such flakes with Landau level spectroscopy in the THz range at very low magnetic fields, we demonstrate a superior electronic quality of these ultralow density layers (n_{0} approximately 3 x 10;{9} cm;{-2}) expressed by the carrier mobility in excess of 10;{7} cm;{2}/(V * s) or scattering time of tau approximately 20 ps. These parameters set new and surprisingly high limits for intrinsic properties of graphene and represent an important challenge for further developments of current graphene technologies.

Molecular nanomagnets and magnetic nanoparticles: the EMR contribution to a common approach.

The current status and future developments of the use of electron magnetic resonance (EMR) for the investigation of magnetic nano-systems is here reviewed. The aim is to stimulate efforts to provide a unified view of the properties of magnetic nanoparticles (MNP) comprising a few hundred magnetic centres, and molecular nanomagnets which contain up to ca. one hundred magnetic centres (MNM). The size of the systems is becoming the same but the approaches to the interpretation of their properties are still different, being bottom up for the latter and top down for the former. We make the point here of the need for a common viewpoint, highlighting the status of the two fields and giving some hints for the future developments. EMR has been a powerful tool for the investigation of magnetic nano-objects and it can provide a tool of fundamental importance for the development of a unified view.

Approaching the dirac point in high-mobility multilayer epitaxial graphene.

Multilayer epitaxial graphene is investigated using far infrared transmission experiments in the different limits of low magnetic fields and high temperatures. The cyclotron-resonance-like absorption is observed at low temperature in magnetic fields below 50 mT, probing the nearest vicinity of the Dirac point. The carrier mobility is found to exceed 250,000 cm2/(V x s). In the limit of high temperatures, the well-defined Landau level quantization is observed up to room temperature at magnetic fields below 1 T, a phenomenon unusual in solid state systems. A negligible increase in the width of the cyclotron resonance lines with increasing temperature indicates that no important scattering mechanism is thermally activated.

High-field/high-frequency EPR studies of spin clusters with integer spin: the multi-frequency approach.

In this paper a rapid overview of the main results obtained from the study with multi-frequency HF-EPR of molecular spin clusters possessing integer spin values is presented. In the first part, two antiferromagnetic rings with zero ground spin state are reported. It is illustrated how the HF-EPR study of the first excited states allows obtaining important information on this kind of spin clusters. In the second part, selected examples of single-molecule magnets (SMM) are treated, starting with complexes involving only a few magnetic ions and going on to more complex systems. Indeed, because of their large zero-field energy gaps, EPR studies of SMM deserve the use of high frequencies and high fields. The approach presented here is twofold. First the interest of studying a series of 'simple' SMM in order to understand the subtle mechanisms underlying their properties is stressed. Then a summary of our HF-EPR studies of the most investigated SMM, Mn12ac and Fe8 is presented.

Multi-frequency EPR and Mössbauer spectroscopic studies on freeze-quenched reaction intermediates of nitric oxide synthase.

It is believed by analogy to chloroperoxidase (CPO) from Caldariomyces fumago that the electronic structure of the intermediate iron-oxo species in the catalytic cycle of nitric oxide synthase (NOS) corresponds to an iron(IV) porphyrin-pi -cation radical. Such species can also be produced by the reaction of ferric NOS with external oxidants within the shunt pathway. We present multi-frequency EPR (9.6, 94, 285 GHz) and Mössbauer spectroscopic studies on freeze-quenched intermediates of the oxygenase domain of nitric oxide synthase which has reacted with peroxy acetic acid within 8-200 ms. The intermediates of the oxygenase domain of both the cytokine inducible NOS (iNOSox) and the neuronal NOS (nNOSox) show an organic radical signal in the 9.6-GHz spectrum overlapping with the spectrum of an unknown species with g-values of 2.24, 2.23 and 1.96. Using 94- and 285-GHz EPR the organic radical signal is assigned to a tyrosine radical on the basis of g-values (i.e. Tyr*562 in nNOSox and Tyr*341 in iNOSox). Mössbauer spectroscopy of (57)Fe-labeled unreacted nNOSox shows a ferric low-spin heme-iron (delta = 0.38 mms(-1), deltaE(Q) = 2.58 mms(-1)). The reaction of nNOSox with peroxy acetic acid for 8 ms leads to the disappearance of the magnetic background characteristic for native nNOSox and a new species with delta = 0.27 mms(-1) and deltaE(Q) = 2.41 mms(-1) is detected at 4.2 K which does not resemble the parameters typical for a Fe(IV) center. It is proposed that this intermediate species corresponds to a ferric low-spin species which magnetically couples to an amino acid radical (presumably Trp*409).

NMR and parity nonconservation. Experimental requirements to observe a difference between enantiomer signals.

The possibility of observing a difference in the high-resolution NMR spectra of two enantiomers as due to parity nonconservation is discussed. Proposals to minimize the NMR linewidths are presented. It is concluded that, using the ultra- high-resolution technique, a difference could be observed with high Z value spin one- half nuclei such as Pt, T1, Xe. Other nuclei can also be considered.

High field EPR studies of mouse ribonucleotide reductase indicate hydrogen bonding of the tyrosyl radical.

Ribonucleotide reductase catalyzes by free radical chemistry the reduction of ribonucleotides to deoxyribonucleotides. The R2 protein of a class 1 ribonucleotide reductase contains a stable tyrosyl radical of neutral phenoxy character, which is necessary for normal enzymatic activity. Here we present the EPR spectra from the tyrosyl free radical in the R2 protein from mouse at 9.62, 115, and 245 GHz. We show that the g-value anisotropy of the mouse R2 radical, when precisely determined from high field EPR spectra, is similar to that of the hydrogen bonded dark stable YD middle dot tyrosyl radical of photosystem II and different from that of the Escherichia coli R2 radical. Because the g-value anisotropy is an important indicator of the hydrogen bonding status of the tyrosyl radical, this result suggests that the mouse R2 radical has its tyrosylate oxygen hydrogen bonded with a D2O exchangeable proton, whereas this hydrogen bond is absent in the E. coli enzyme. It is suggested that the observed proton may be derived from the tyrosine that will become a tyrosyl radical.

The tyrosyl free radical of recombinant ribonucleotide reductase from Mycobacterium tuberculosis is located in a rigid hydrophobic pocket.

The tyrosyl free radical in protein R2-2 of class Ib ribonucleotide reductase (RNR) fromMycobacterium tuberculosis is essential for the enzymatic activity and has an EPR spectrum remarkably similar to that of the tyrosyl radical YD* in PSII. The EPR relaxation properties of the radical suggest a very weak exchange coupling between the two redox centers, the radical and the diferric cluster. The tyrosyl radical gives almost identical EPR spectra in the temperature interval 10-293 K. We conclude that the tyrosyl radical sits in a rigid pocket. Two ring protons and one beta-methylene proton account for the major anisotropic hyperfine interactions. A high-frequency EPR spectrum of the radical showed a resolved gx = 2. 0092, indicating that a hydrogen bond to the phenolic oxygen of the radical is absent. Theoretical modeling studies based on the structural data known for Salmonella typhimurium class Ib RNR protein R2F revealed a hydrophobic wall aligned with the radical harboring residue Y110. The distance between the phenolic oxygen of the radical and the diferric cluster is longer in the two class Ib nrdF R2 proteins than in other characterized class Ia R2 proteins. The tyrosyl radical in protein R2-2 from M. tuberculosis was accessible to direct reduction by dithionite in the absence of a mediator. The radical could be partly regenerated when the system was exposed to O2 after the completion of anaerobic reduction. This indicates that the Fe3+ ions also had become reduced by dithionite.

Origin of second-order transverse magnetic anisotropy in Mn12-acetate.

The symmetry breaking effects for quantum tunneling of the magnetization in Mn12-acetate, a molecular nanomagnet, represent an open problem. We present structural evidence that the disorder of the acetic acid of crystallization induces sizable distortion of the Mn(III) sites, giving rise to six different isomers. Four isomers have symmetry lower than tetragonal and a nonzero second-order transverse magnetic anisotropy, which has been evaluated using a ligand field approach. The result of the calculation leads to an improved simulation of electron paramagnetic resonance spectra and justifies the tunnel splitting distribution derived from the field sweep rate dependence of the hysteresis loops.

Restoring proper radical generation by azide binding to the iron site of the E238A mutant R2 protein of ribonucleotide reductase from Escherichia coli.

The enzyme activity of Escherichia coli ribonucleotide reductase requires the presence of a stable tyrosyl free radical and diiron center in its smaller R2 component. The iron/radical site is formed in a reconstitution reaction between ferrous iron and molecular oxygen in the protein. The reaction is known to proceed via a paramagnetic intermediate X, formally a Fe(III)-Fe(IV) state. We have used 9.6 GHz and 285 GHz EPR to investigate intermediates in the reconstitution reaction in the iron ligand mutant R2 E238A with or without azide, formate, or acetate present. Paramagnetic intermediates, i.e. a long-living X-like intermediate and a transient tyrosyl radical, were observed only with azide and under none of the other conditions. A crystal structure of the mutant protein R2 E238A/Y122F with a diferrous iron site complexed with azide was determined. Azide was found to be a bridging ligand and the absent Glu-238 ligand was compensated for by azide and an extra coordination from Glu-204. A general scheme for the reconstitution reaction is presented based on EPR and structure results. This indicates that tyrosyl radical generation requires a specific ligand coordination with 4-coordinate Fe1 and 6-coordinate Fe2 after oxygen binding to the diferrous site.

High-frequency EPR study of a new mononuclear manganese(III) complex:. [(terpy)Mn(N3)3] (terpy = 2,2':6',2''-terpyridine).

The isolation and structural characterization of [(terpy)Mn(III)(N3)3], complex 1, is reported (terpy = 2,2':6',2' '-terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer [(terpy)(H2O)Mn(III)(O)2Mn(IV)(OH2)(terpy)](NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) A, b = 8.9007(2) A, c = 12.109(2) A, alpha = 93.79(1) degrees, beta = 103.17(1) degrees, gamma = 103.11(1) degrees, and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The nu(asym)(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm(-1) with a less intense feature at 2072 cm(-1), and in the FT-Raman as a strong band at 2071 cm(-1) with a weaker broad band at 2046 cm(-1). The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (+/-0.01) cm(-1), E = 0.48 (+/-0.01) cm(-1), E '= 0.53 (+/-0.01) cm(-1), g(x) = 2.00 (+/-0.005), g(y) = 1.98 (+/-0.005), g(z) = 2.01 (+/-0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D < 0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (+/-0.01) cm(-1), E = 0.51 (+/-0.01) cm(-1), g(x) = 2.00 (+/-0.005), g(y) = 1.98 (+/-0.005), and g(z) = 2.01 (+/-0.005).