Microscopic evaluation of spin and orbital moment in ferromagnetic resonance.

Time-resolved X-ray magnetic circular dichroism under the effects of ferromagnetic resonance (FMR), known as X-ray ferromagnetic resonance (XFMR) measurements, enables direct detection of precession dynamics of magnetic moment. Here we demonstrated XFMR measurements and Bayesian analyses as a quantitative probe for the precession of spin and orbital magnetic moments under the FMR effect. Magnetization precessions in two different Pt/Ni-Fe thin film samples were directly detected. Furthermore, the ratio of dynamical spin and orbital magnetic moments was evaluated quantitatively by Bayesian analyses for XFMR energy spectra around the Ni L 2 , 3 absorption edges. Our study paves the way for a microscopic investigation of the contribution of the orbital magnetic moment to magnetization dynamics.

Time-resolved resonant soft X-ray scattering combined with MHz synchrotron X-ray and laser pulses at the Photon Factory.

A picosecond pump-probe resonant soft X-ray scattering measurement system has been developed at the Photon Factory storage ring for highly efficient data collection. A high-repetition-rate high-power compact laser system has been installed to improve efficiency via flexible data acquisition to a sub-MHz frequency in time-resolved experiments. Data are acquired by gating the signal of a channel electron multiplier with a pulse-counting mode capable of discriminating single-bunch soft X-ray pulses in the dark gap of the hybrid operation mode in the storage ring. The photoinduced dynamics of magnetic order for multiferroic manganite SmMn2O5 are clearly demonstrated by the detection of transient changes in the resonant soft X-ray scattering intensity around the Mn LIII- and O K-edges.

Entropy-Assisted, Long-Period Stacking of Honeycomb Layers in an AlB2-Type Silicide.

Configurational entropy can impact crystallization processes, tipping the scales between structures of nearly equal internal energy. Using alloyed single crystals of Gd2PdSi3 in the AlB2-type structure, we explore the formation of complex layer sequences made from alternating, two-dimensional triangular and honeycomb slabs. A four-period and an eight-period stacking sequence are found to be very close in internal energy, the latter being favored by entropy associated with covering the full configuration space of interlayer bonds. Possible consequences of polytype formation on magnetism in Gd2PdSi3 are discussed.

Conceptual design of the Hybrid Ring with superconducting linac.

The Hybrid Ring with a superconducting-linac injector as a highly flexible synchrotron radiation source to enable new experimental techniques and enhance many existing ones is proposed. It is designed to be operated with the coexistence of the storage (SR) bunches characterized by the performance of the storage ring, and the single-pass (SP) bunches characterized by the performance of the superconducting linac. Unique experiments can be performed by simultaneous use of the SR and SP beams, in addition to research with various experimental techniques utilizing the versatile SR beam and research in the field of ultrafast dynamics utilizing the ultrashort pulse of the SP beam. The extendability of the Hybrid Ring will allow it to be developed into a synchrotron radiation complex.

Topological charge of soft X-ray vortex beam determined by inline holography.

A Laguerre-Gaussian (LG) vortex beam having a spiral wavefront can be characterized by its topological charge (TC). The TC gives the number of times that the beam phase passes through the interval [Formula: see text] following a closed loop surrounding the propagation axis. Here, the TC spectra of soft X-ray vortex beams are acquired using the in-line holography technique, where interference between vortex waves produced from a fork grating and divergent waves from a Fresnel zone plate is observed as a holographic image. The analyses revealed the phase distributions and the TC for the LG vortex waves, which reflects topological number of the fork gratings, as well as for the Hermite-Gaussian (HG) mode waves generated from the other gratings. We also conducted a simulation of the present technique for pair annihilation of topological defects in a magnetic texture. These results may pave the way for development of probes capable of characterizing the topological numbers of magnetic defects.

Zoology of Multiple-Q Spin Textures in a Centrosymmetric Tetragonal Magnet with Itinerant Electrons.

Magnetic skyrmion is a topologically stable particle-like swirling spin texture potentially suitable for high-density information bit, which was first observed in noncentrosymmetric magnets with Dzyaloshinskii-Moriya interaction. Recently, nanometric skyrmion has also been discovered in centrosymmetric rare-earth compounds, and the identification of their skyrmion formation mechanism and further search of nontrivial spin textures are highly demanded. Here, magnetic structures in a prototypical skyrmion-hosting centrosymmetric tetragonal magnet GdRu2 Si2 is exhaustively studied by performing the resonant X-ray scattering experiments. A rich variety of double-Q magnetic structures, including the antiferroic order of meron(half-skyrmion)/anti-meron-like textures with fractional local topological charges are identified. The observed intricate magnetic phase diagram is successfully reproduced by the theoretical framework considering the four-spin interaction mediated by itinerant electrons and magnetic anisotropy. The present results will contribute to the better understanding of the novel skyrmion formation mechanism in this centrosymmetric rare-earth compound, and suggest that itinerant electrons can ubiquitously host a variety of unique multiple-Q spin orders in a simple crystal lattice system.

X-ray study of ferroic octupole order producing anomalous Hall effect.

Recently found anomalous Hall, Nernst, magnetooptical Kerr, and spin Hall effects in the antiferromagnets Mn3X (X = Sn, Ge) are attracting much attention for spintronics and energy harvesting. Since these materials are antiferromagnets, the origin of these functionalities is expected to be different from that of conventional ferromagnets. Here, we report the observation of ferroic order of magnetic octupole in Mn3Sn by X-ray magnetic circular dichroism, which is only predicted theoretically so far. The observed signals are clearly decoupled with the behaviors of uniform magnetization, indicating that the present X-ray magnetic circular dichroism is not arising from the conventional magnetization. We have found that the appearance of this anomalous signal coincides with the time reversal symmetry broken cluster magnetic octupole order. Our study demonstrates that the exotic material functionalities are closely related to the multipole order, which can produce unconventional cross correlation functionalities.

Topological Nernst Effect of the Two-Dimensional Skyrmion Lattice.

The topological Hall effect (THE) and its thermoelectric counterpart, the topological Nernst effect (TNE), are hallmarks of the skyrmion lattice phase (SkL). We observed the giant TNE of the SkL in centrosymmetric Gd_{2}PdSi_{3}, comparable in magnitude to the largest anomalous Nernst signals in ferromagnets. Significant enhancement (suppression) of the THE occurs when doping electrons (holes) to Gd_{2}PdSi_{3}. On the electron-doped side, the topological Hall conductivity approaches the characteristic threshold ∼1000 (Ω cm)^{-1} for the intrinsic regime. We use the filling-controlled samples to confirm Mott's relation between TNE and THE and discuss the importance of Gd-5d orbitals for transport in this compound.

Nanometric square skyrmion lattice in a centrosymmetric tetragonal magnet.

Magnetic skyrmions are topologically stable spin swirls with a particle-like character and are potentially suitable for the design of high-density information bits. Although most known skyrmion systems arise in non-centrosymmetric systems with a Dzyaloshinskii-Moriya interaction, centrosymmetric magnets with a triangular lattice can also give rise to skyrmion formation, with a geometrically frustrated lattice being considered essential in this case. Until now, it remains an open question if skyrmions can also exist in the absence of both geometrically frustrated lattice and inversion symmetry breaking. Here we discover a square skyrmion lattice state with 1.9 nm diameter skyrmions in the centrosymmetric tetragonal magnet GdRu2Si2 without a geometrically frustrated lattice by means of resonant X-ray scattering and Lorentz transmission electron microscopy experiments. A plausible origin of the observed skyrmion formation is four-spin interactions mediated by itinerant electrons in the presence of easy-axis anisotropy. Our results suggest that rare-earth intermetallics with highly symmetric crystal lattices may ubiquitously host nanometric skyrmions of exotic origins.

Skyrmion phase and competing magnetic orders on a breathing kagomé lattice.

Magnetic skyrmion textures are realized mainly in non-centrosymmetric, e.g. chiral or polar, magnets. Extending the field to centrosymmetric bulk materials is a rewarding challenge, where the released helicity/vorticity degree of freedom and higher skyrmion density result in intriguing new properties and enhanced functionality. We report here on the experimental observation of a skyrmion lattice (SkL) phase with large topological Hall effect and an incommensurate helical pitch as small as 2.8 nm in metallic Gd3Ru4Al12, which materializes a breathing kagomé lattice of Gadolinium moments. The magnetic structure of several ordered phases, including the SkL, is determined by resonant x-ray diffraction as well as small angle neutron scattering. The SkL and helical phases are also observed directly using Lorentz-transmission electron microscopy. Among several competing phases, the SkL is promoted over a low-temperature transverse conical state by thermal fluctuations in an intermediate range of magnetic fields.

Skyrmion lattice with a giant topological Hall effect in a frustrated triangular-lattice magnet.

Geometrically frustrated magnets can host complex spin textures, leading to unconventional electromagnetic responses. Magnetic frustration may also promote topologically nontrivial spin states such as magnetic skyrmions. Experimentally, however, skyrmions have largely been observed in noncentrosymmetric lattice structures or interfacial symmetry-breaking heterostructures. Here, we report the emergence of a Bloch-type skyrmion state in the frustrated centrosymmetric triangular-lattice magnet Gd2PdSi3 We observed a giant topological Hall response, indicating a field-induced skyrmion phase, which is further corroborated by the observation of in-plane spin modulation probed by resonant x-ray scattering. Our results may lead to further discoveries of emergent electrodynamics in magnetically frustrated centrosymmetric materials.

Abundance of Common Aerobic Anoxygenic Phototrophic Bacteria in a Coastal Aquaculture Area.

Aerobic anoxygenic phototrophic bacteria (AAnPB) rely on not only heterotrophic but also phototrophic energy gain. AAnPB are known to have high abundance in oligotrophic waters and are the major portion of the bacterial carbon stock in the environment. In a yearlong study in an aquaculture area in the Uwa Sea, Japan, AAnPB, accounted for 4.7 to 24% of the total bacteria by count. Since the cell volume of AAnPB is 2.23 ± 0.674 times larger than the mean for total bacteria, AAnPB biomass is estimated to account for 10-53% of the total bacterial assemblage. By examining pufM gene sequence, a common phylogenetic AAnPB species was found in all sampling sites through the year. The common species and other season-specific species were phylogenetically close to unculturable clones recorded in the Sargasso Sea and Pacific Ocean. The present study suggests that the common species may be a cosmopolitan species with worldwide distribution that is abundant not only in the oligotrophic open ocean but also in eutrophic aquaculture areas.

Quantum Hall effect in a bulk antiferromagnet EuMnBi2 with magnetically confined two-dimensional Dirac fermions.

For the innovation of spintronic technologies, Dirac materials, in which low-energy excitation is described as relativistic Dirac fermions, are one of the most promising systems because of the fascinating magnetotransport associated with extremely high mobility. To incorporate Dirac fermions into spintronic applications, their quantum transport phenomena are desired to be manipulated to a large extent by magnetic order in a solid. We report a bulk half-integer quantum Hall effect in a layered antiferromagnet EuMnBi2, in which field-controllable Eu magnetic order significantly suppresses the interlayer coupling between the Bi layers with Dirac fermions. In addition to the high mobility of more than 10,000 cm(2)/V s, Landau level splittings presumably due to the lifting of spin and valley degeneracy are noticeable even in a bulk magnet. These results will pave a route to the engineering of magnetically functionalized Dirac materials.

Solid-solid phase interconversion in an organic conductor crystal: hydrogen-bond-mediated dynamic changes in π-stacked molecular arrangement and physical properties.

Solid-solid phase interconversion was observed in an organic conductor based on a hydrogen-bonded (H-bonded) TTF (tetrathiafulvalene) molecular unit, in which the π-stacked molecular arrangement and physical properties were dynamically changed with unexpected transformation of the H-bond unit between the planar and bent forms.

Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal.

A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

Protonation of pyridyl-substituted TTF derivatives: substituent effects in solution and in the proton-electron correlated charge-transfer complexes.

Protonated pyridyl-substituted tetrathiafulvalene electron-donor molecules (PyH(+)-TTF) showed significant changes in the electron-donating ability and HOMO-LUMO energy gap compared to the neutral analogues and gave a unique N(+)-H⋅⋅⋅N hydrogen-bonded (H-bonded) dimer unit in the proton-electron correlated charge-transfer (CT) complex crystals. We have evaluated these features from the viewpoint of the molecular structure of the PyH(+)-TTF derivatives, that is, the substitution position of the Py group and/or the presence or absence of the ethylenedithio (EDT) group. Among 2-PyH(+)-TTF (1 oH(+)), 3-PyH(+)-TTF (1 mH(+)), 4-PyH(+)-TTF (1 pH(+)), and 4-PyH(+)-EDT-TTF (2 pH(+)) systems, the para-pyridyl-substituted donors 1 pH(+) and 2 pH(+) exhibit more marked changes upon protonation in solution; a larger redshift in the intramolecular CT absorption band and a larger decrease in the electron-donating ability. Furthermore, the EDT system 2 pH(+) has the smallest intramolecular Coulombic repulsion energy. These differences are reasonably interpreted by considering the energy levels and distributions of the HOMO and LUMO obtained by quantum chemical calculations. Such substituent effects related to protonation were also examined by comparing the structure and properties of a new H-bonded CT complex crystal based on 2 pH(+) with those of its 1 pH(+) analogue recently prepared by us: Both of them form a similar type of H-bonded dimer unit, however, its charge distribution as well as the overall molecular arrangement, electronic structure, and conductivity were significantly modulated by the introduction of the EDT group. These results provide a new insight into the structural and electronic features of the PyH(+)-TTF-based proton-electron correlated molecular conductors.

X-ray-induced phase transitions by selective excitation of heterometal ions in a cyanide-bridged Fe-Co molecular square.

A cyanide-bridged tetranuclear Fe-Co complex showed electron-transfer-coupled spin transitions induced by X-ray irradiation. Single crystal X-ray diffraction measurements and X-ray absorption spectroscopy revealed that the X-ray-induced phase transition ratio was significantly altered by the selective excitation of the metal ions.

Hydrogen bond-promoted metallic state in a purely organic single-component conductor under pressure.

Purely organic materials are generally insulating. Some charge-carrier generation, however, can provide them with electrical conductivity. In multi-component organic systems, carrier generation by intermolecular charge transfer has given many molecular metals. By contrast, in purely organic single-component systems, metallic states have rarely been realized although some neutral-radical semiconductors have been reported. Here we uncover a new type of purely organic single-component molecular conductor by utilizing strong hydrogen-bonding interactions between tetrathiafulvalene-based electron-donor molecules. These conductors are composed of highly symmetric molecular units constructed by the strong intra-unit hydrogen bond. Moreover, we demonstrate that, in this system, charge carriers are produced by the partial oxidation of the donor molecules and delocalized through the formation of the symmetric intra-unit hydrogen bonds. As a result, our conductors show the highest room-temperature electrical conductivity and the metallic state under the lowest physical pressure among the purely organic single-component systems, to our knowledge.

Charge-order driven proton arrangement in a hydrogen-bonded charge-transfer complex based on a pyridyl-substituted TTF derivative.

A unique N(+)-H···N hydrogen-bonded (H-bonded) dimer motif based on partially oxidized pyridyl-substituted TTF was constructed in the charge-transfer complex. The charge ordering in the TTF column by the charge disproportionation in the dimer regulates the arrangement of the H-bonded proton, evidencing the proton-electron coupled state.

Controlled intramolecular electron transfers in cyanide-bridged molecular squares by chemical modifications and external stimuli.

A series of cyanide bridged Fe-Co molecular squares, [Co(2)Fe(2)(CN)(6)(tp*)(2)(dtbbpy)(4)](PF(6))(2)·2MeOH (1), [Co(2)Fe(2)(CN)(6)(tp*)(2)(bpy)(4)](PF(6))(2)·2MeOH (2), and [Co(2)Fe(2)(CN)(6)(tp)(2)(dtbbpy)(4)](PF(6))(2)·4H(2)O (3) (tp = hydrotris(pyrazol-1-yl)borate, tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate, bpy =2,2'-bipyridine, dtbbpy =4,4'-di-tert-butyl-2,2'-bipyridine), were prepared by the reactions of [Fe(CN)(3)(L)](-) (L = tp or tp*) with Co(2+) and bidentate ligands (bpy or dtbbpy) in MeOH. In the molecular squares, Fe and Co ions are alternately bridged by cyanide ions, forming macrocyclic tetranuclear cores. Variable temperature X-ray structural analyses and magnetic susceptibility measurements confirmed that 1 exhibits two-step charge-transfer induced spin transitions (CTIST) centered at T(1/2) = 275 and 310 K in the solid state. The Fe and Co ions in 1 are the low-spin (LS) Fe(III) and high-spin (HS) Co(II) ions, described here in the high-temperature (HT) phase ([Fe(III)(LS2)Co(II)(HS2)]) at 330 K, while a low-temperature (LT) phase ([Fe(II)(LS2)Co(III)(LS2)]) with LS Fe(II) and Co(III) ions was dominant below 260 K. X-ray structural analysis revealed that in the intermediate (IM) phase at 298 K 1 exhibits positional ordering of [Fe(III)(LS2)Co(II)(HS2)] and [Fe(II)(LS2)Co(III)(LS2)] species with the 2:2 ratio. In photomagnetic experiments on 1, light-induced CTIST from the LT to the HT phase was observed by excitation of Fe(II) → Co(III) intervalence charge transfer (IVCT) band at 5 K and the trapped HT phase thermally relaxed to the LT phase in a two-step fashion. On the other hand, 2 and 3 are in the HT and LT phases, respectively, throughout the entire temperature range measured, and no CTIST was observed. UV-vis-NIR absorption spectral measurements and cyclic voltammetry in solution revealed that the different electronic states in 1-3 are ascribable to the destabilization of iron and cobalt ion d-orbitals by the introduction of methyl and tert-butyl groups to the ligands tp and bpy, respectively. Temperature dependence of UV-vis-NIR spectra confirmed that 1 exhibited a one-step CTIST in butyronitrile, of which T(1/2) varied from 227 to 280 K upon the addition of trifluoroacetic acid.