J. C. Cezar

Quantum tunnelling of the magnetization in a monolayer of oriented single-molecule magnets

A fundamental step towards atomic- or molecular-scale spintronic devices has recently been made by demonstrating that the spin of an individual atom deposited on a surface, or of a small paramagnetic molecule embedded in a nanojunction, can be externally controlled. An appealing next step is the extension of such a capability to the field of information storage, by taking advantage of the magnetic bistability and rich quantum behaviour of single-molecule magnets (SMMs). Recently, a proof of concept that the magnetic memory effect is retained when SMMs are chemically anchored to a metallic surface was provided. However, control of the nanoscale organization of these complex systems is required for SMMs to be integrated into molecular spintronic devices. Here we show that a preferential orientation of Fe4 complexes on a gold surface can be achieved by chemical tailoring. As a result, the most striking quantum feature of SMMs—their stepped hysteresis loop, which results from resonant quantum tunnelling of the magnetization—can be clearly detected using synchrotron-based spectroscopic techniques. With the aid of multiple theoretical approaches, we relate the angular dependence of the quantum tunnelling resonances to the adsorption geometry, and demonstrate that molecules predominantly lie with their easy axes close to the surface normal. Our findings prove that the quantum spin dynamics can be observed in SMMs chemically grafted to surfaces, and offer a tool to reveal the organization of matter at the nanoscale.

Valence, spin, and orbital state of Co ions in one-dimensional Ca3Co2O6 : An x-ray absorption and magnetic circular dichroism study

We have investigated the valence, spin, and orbital state of the Co ions in the one-dimensional cobaltate Ca3Co2O6 using x-ray absorption and x-ray magnetic circular dichroism at the Co-L2,3 edges. The Co ions at both the octahedral Cooct and trigonal Cotrig sites are found to be in a 3+ state. From the analysis of the dichroism we established a low-spin state for the Cooct and a high-spin state with an anomalously large orbital moment of 1.7B at the Co trig ions. This large orbital moment along the c-axis chain and the unusually large magnetocrystalline anisotropy can be traced back to the double occupancy of the d2 orbital in trigonal crystal field.

X-ray absorption and x-ray magnetic dichroism study on Ca3CoRhO6 and Ca3FeRhO6

Using x-ray absorption spectroscopy at the Rh-L_2,3, Co-L_2,3, and Fe-L_2,3 edges, we find a valence state of Co^2+/Rh^4+ in Ca3CoRhO6 and of Fe^3+/Rh^3+ in Ca3FeRhO6. X-ray magnetic circular dichroism spectroscopy at the Co-L_2,3 edge of Ca3CoRhO6 reveals a giant orbital moment of about 1.7mu_B, which can be attributed to the occupation of the minority-spin d_0d_2 orbital state of the high-spin Co^2+ (3d^7) ions in trigonal prismatic coordination. This active role of the spin-orbit coupling explains the strong magnetocrystalline anisotropy and Ising-like magnetism of Ca3CoRhO6.

Pressure-Induced Magnetic Switching and Linkage Isomerism in K0.4Fe4(Cr(CN)6)2.8 ·16H2O: X-ray Absorption and Magnetic Circular Dichroism Studies

The effect of applied pressure on the magnetic properties of the Prussian blue analogue K0.4Fe4[Cr(CN)6]2.8 x 16 H2O (1) has been analyzed by dc and ac magnetic susceptibility measurements. Under ambient conditions, 1 orders ferromagnetically at a critical temperature (T(C)) of 18.5 K. Under application of pressure in the 0-1200 MPa range, the magnetization of the material decreases and its critical temperature shifts to lower temperatures, reaching T(C) = 7.5 K at 1200 MPa. Pressure-dependent Raman and Mossbauer spectroscopy measurements show that this striking behavior is due to the isomerization of some Cr(III)-C[triple bond]N-Fe(II) linkages to the Cr(III)-N[triple bond]C-Fe(II) form. As a result, the ligand field around the iron(II) centers increases, and the diamagnetic low-spin state is populated. As the number of diamagnetic centers in the cubic lattice increases, the net magnetization and critical temperature of the material decrease considerably. The phenomenon is reversible: releasing the pressure restores the magnetic properties of the original material. However, we have found that under more severe pressure conditions, a metastable sample containing 22% Cr(III)-N[triple bond]C-Fe(II) linkages can be obtained. X-ray absorption spectroscopy and magnetic circular dichroism of this metastable sample confirm the linkage isomerization process.

X‐Ray Detected Magnetic Hysteresis of Thermally Evaporated Terbium Double‐Decker Oriented Films

Fabrication of molecular nanostructures and control of the molecular properties at the nanoscale is at the basis of the development of innovative single molecule devices. [ 1 ] Particularly active is the research for the organization of single molecule magnets (SMMs) that have been proposed as ideal candidates for the development of molecular spintronics and data storage devices. [ 2 , 3 ] These molecules are a well known class of compounds characterized by the peculiar presence of a strong axial magnetic anisotropy that induces a slow relaxation in the magnetization and a magnetic hysteresis of molecular origin showing spectacular quantum effects. [ 4 ] Thanks to the surface sensitivity of synchrotron-based techniques it has been possible to provide the proof of concept that SMM behavior is observable in a single layer of magnetic molecules. [ 5 ] First attempts to control at the nanoscale the SMM assembling have been made by opportune functionalization promoting their grafting on specifi c surfaces in order to form monolayer deposits from solution. [ 6 , 7 ] However, cleaner processes, e.g. thermal evaporation, [ 8 ] are required for the development of real devices or to extend the investigation to reactive surfaces, e.g. ferromagnetic metals, and

Ising Magnetism and Ferroelectricity in Ca3CoMnO6

The origin of both the Ising chain magnetism and ferroelectricity in Ca3CoMnO6 is studied by ab initio electronic structure calculations and x-ray absorption spectroscopy. We find that Ca3CoMnO6 has alternate trigonal prismatic Co2+ and octahedral Mn4+ sites in the spin chain. Both the Co2+ and Mn4+ are in the high-spin state. In addition, the Co2+ has a huge orbital moment of 1.7micro_{B} which is responsible for the significant Ising magnetism. The centrosymmetric crystal structure known so far is calculated to be unstable with respect to exchange striction in the experimentally observed upward arrow upward arrow downward arrow downward arrow antiferromagnetic structure for the Ising chain. The calculated inequivalence of the Co-Mn distances accounts for the ferroelectricity.

Spin and orbital Ti magnetism at LaMnO3/SrTiO3 interfaces

In systems with strong electron-lattice coupling, such as manganites, orbital degeneracy is lifted, causing a null expectation value of the orbital magnetic moment. Magnetic structure is thus determined by spin-spin superexchange. In titanates, however, with much smaller Jahn-Teller distortions, orbital degeneracy might allow non-zero values of the orbital magnetic moment, and novel forms of ferromagnetic superexchange interaction unique to t(2g) electron systems have been theoretically predicted, although their experimental observation has remained elusive. In this paper, we report a new kind of Ti(3+) ferromagnetism at LaMnO(3)/SrTiO(3) epitaxial interfaces. It results from charge transfer to the empty conduction band of the titanate and has spin and orbital contributions evidencing the role of orbital degeneracy. The possibility of tuning magnetic alignment (ferromagnetic or antiferromagnetic) of Ti and Mn moments by structural parameters is demonstrated. This result will provide important clues for understanding the effects of orbital degeneracy in superexchange coupling.

Soft‐X‐ray‐Induced Redox Isomerism in a Cobalt Dioxolene Complex

Valence tautomerism (VT) defines reversible interconversions between two or more redox isomers. It is established that these interconversions can be stimulated by temperature and light irradiation. For example, the diamagnetic [Co(Me2tpa)(DBCat)]PF6·C6H5CH3 complex (1) (Me2tpa = bis(6-methyl-(2-pyridylmethyl)) (2-pyridylmethyl)amine, DBCat = 3,5-di-tert-butylcatecholato) was found to undergo a thermally induced interconversion in the solid state yielding the redox isomer characterized by the high-spin Co-semiquinonato (hs-Co-SQ) charge distribution (see Scheme 1). 3] The observed transition can be formally described as the result of an entropy-driven intramolecular electron transfer involving the donor catecholato and the cobalt(III) acceptor. At cryogenic temperatures, laser irradiation of the solid compound at 904 nm, where a ligand-tometal charge transfer (LMCT) occurs, was found by bulk magnetic measurements to induce the same process, affording the hs-Co-semiquinonato species as a metastable phase in 90% yield with a rather long lifetime (two weeks at 9 K). Soft X-ray absorption spectroscopy (XAS) is an elementsensitive synchrotron-based technique and provides a powerful tool to study the electronic and chemical structure of a specific atom and its coordination environment. It is particularly powerful in the magnetic study of 3d metal complexes. With the additional asset of very high detection sensitivity, XAS has been effectively used in the characterization of systems with multiple quasi degenerated electronic states, including very diluted and nanostructured systems. We have found that for 1 this technique not only yields this important information, but also intrinsically provides the perturbation for inducing interconversion between the two redox isomers. This is an unprecedented result and we believe it to be particularly important for the study of all the complexes exhibiting photochromism. Figure 1 shows the temperature dependence of the cobalt L3-edge X-ray absorption spectra of 1 (the L2,3 spectra are shown in Figure S1 of the Supporting Information). The spectra were obtained with a X-ray flux of 10 photons s 1 on Scheme 1. The two different electronic configurations involved in VT process.

Electronic structure of Cu-doped ZnO thin films by x-ray absorption, magnetic circular dichroism, and resonant inelastic x-ray scattering

The electronic structure of Cu-doped ZnO thin films, synthesized with a nominal composition of Zn1−xCuxO (x=0.03, 0.05, 0.07, and 0.10) by using spray pyrolysis method, has been investigated using near-edge x-ray absorption fine structure (NEXAFS) experiments at the O K- and the Cu L3,2-edges and resonant inelastic x-ray scattering (RIXS) measurements at Cu L3,2 edge. The Zn1−xCuxO thin films showed single phase wurtzite-hexagonal like crystal structure and ferromagnetic behavior at room temperature (RT). The intensity of the pre-edge spectral feature at the O K-edge increases with the Cu concentration, which clearly reveals that there is strong hybridization of O 2p–Cu 3d orbitals in the ZnO matrix. Spectral features of the Cu L3,2-edge NEXAFS exhibit multiple absorption peaks and appreciable x-ray magnetic circular dichroism signal that persists even at RT. These results demonstrate that Cu is in mixed valence state of Cu2+,3+/Cu1+, substituting at the Zn site and Cu2+/3+ ions are magnetically polarized...

Direct quantification of gold along a single Si nanowire.

The presence of gold on the sidewall of a tapered, single silicon nanowire is directly quantified from core-level nanospectra using energy-filtered photoelectron emission microscopy. The uniform island-type partial coverage of gold determined as 0.42+/-0.06 (approximately 1.8 ML) is in quantitative agreement with the diameter reduction of the gold catalyst observed by scanning electron microscopy and is confirmed by a splitting of the photothresholds collected from the sidewall, from which characteristic local work functions are extracted using a model of the full secondary electron distributions.