Charge/orbital ordering structure of Pr(1-x)Ca(x)MnO(3)(x = 3/8) examined by low-temperature transmission electron microscopy

The structural phase transition of Pr(1-x)Ca(x)MnO(3)(x = 3/8) was investigated by means of low-temperature transmission electron microscopy. Superlattice reflection spots with a modulation wave vector q(1) = (0,1/2,0) appeared below 230 K, indicating formation of the d(3x(2-r(2))/d(3y(2)-r(2)) type of charge/orbital ordering. Below 150 K, a new series of superlattice reflection spots with a modulation wave vector q(2) = (1/4,1/4,1/2) appeared, suggesting an additional ordering of excess 1/8 Mn(3+), necessary due to the deviation of x from 1/2, with the occupation of the d(3z(2-r(2)) type of e(g) orbital.     

红色荧光粉Na_zCa_(1-x-2y-z)Bi_yMoO_4∶Eu_(x+y)~(3+)发光研究

采用高温固相法制备系列红色荧光粉NazCa1-x-2y-zBiyMoO4∶Eux3++y(y,z=0,x=0.24,0.26,0.30,0.34,0.38;x=0.30,y=0.01,0.02,0.03,0.04,0.05,0.06,0.07,z=0;x=0.30,y=0.04,z=0.38)。用X射线粉末衍射(XRD)法测试了所制样品晶相结构。采用荧光光谱仪对样品的发光性能进行了表征,结果表明:当Eu3+单掺杂量浓度x=0.30时,荧光粉(Ca0.70MoO4∶Eu03.+30)的发光强度最强;当Eu3+-Bi3+共掺杂量浓度y=0.03时,电荷迁移带(CTB)强度达到最强,而对于Eu3+特征发射峰,当共掺杂浓度y<0.03时,位于393 nm处的激发峰强度比464 nm强,共掺浓度y>0.03时,464 nm峰比393 nm峰强,共掺浓度为y=0.04时,393和464 nm处两峰位置强度都达到最强。作为电荷补尝剂的Na2CO3掺入上述荧光粉中后,荧光粉激发和发射强度明显地增强。结果表明,通过调节Bi3+/Eu3+掺杂比例可以改变位于近紫外光393 nm和蓝光区464 nm处激发光相对强度。     

Hidden magnetic configuration in epitaxial La(1-x) Sr(x) MnO3 films

We present an unreported magnetic configuration in epitaxial La(1-x) Sr(x) MnO3 (x ～ 0.3) (LSMO) films grown on strontium titanate (STO). X-ray magnetic circular dichroism indicates that the remanent magnetic state of thick LSMO films is opposite to the direction of the applied magnetic field. Spectroscopic and scattering measurements reveal that the average Mn valence varies from mixed Mn(3+)/Mn(4+) to an enriched Mn3+ region near the STO interface, resulting in a compressive lattice along the a, b axis and a possible electronic reconstruction in the Mn e(g) orbital (d(3)z(2)-r(2). This reconstruction may provide a mechanism for coupling the Mn3+ moments antiferromagnetically along the surface normal direction, and in turn may lead to the observed reversed magnetic configuration.     

Ferromagnetic fluctuation and possible triplet superconductivity in NaxCoO2.yH2O: fluctuation-exchange study of the multiorbital Hubbard model

Spin and charge fluctuations and superconductivity in NaxCoO2.yH(2)O are studied based on a multiorbital Hubbard model. Tight-binding parameters are determined to reproduce the results of band calculations. By applying the fluctuation-exchange approximation, we show that the Hund's-rule coupling between the Co t(2g) orbitals causes ferromagnetic (FM) spin fluctuation. Triplet fy((y(2)-3x(2)))-wave and p-wave pairings are favored by this FM fluctuation on the hole-pocket band. We propose that, in NaxCoO2.yH(2)O, the Co t(2g) orbitals and interorbital Hund's-rule coupling play important roles on the triplet pairing, and this compound can be a first example of the triplet superconductor in which the orbital degrees of freedom play substantial roles.     

O1s and Mn2p NEXAFS on single-layered La1-xSr1+xMnO4: crystal field effect versus orbital coupling mechanism

O1s and Mn2p near-edge X-ray absorption spectroscopy on La_1-xSr_1+xMnO₄ (0 ≤x ≤0.5) single crystals shows that Sr doping does not only provide holes to the system but also induces a continuous transfer of electrons from out-of-plane d_3z2-r2 to in-plane d_3x2-r2/d_3y2-r2 orbitals. Furthermore, a non-vanishing electron occupation of in-plane d_x2-y2 and out-of-plane d_3z2-r2 orbitals is observed up to relatively high doping contents. These findings demonstrate that the energy difference between all these orbital types has to be very small and manifest that the orbital degree of freedom is determined not just by crystal field effects but also by orbital coupling. Moreover, the doping-dependent transfer of spectral weight observed in the current data identifies La_1-xSr_1+xMnO₄ as a charge-transfer insulator.     

Electronic structure of charge- and spin-controlled Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3

We present the electronic structure of Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3 investigated by high-resolution photoemission spectroscopy. In the vicinity of the Fermi level, it was found that the electronic structure was composed of a Cr 3d local state with the t(2g)3 configuration and a Ti 3d itinerant state. The energy levels of these Cr and Ti 3d states are well interpreted by the difference of the charge-transfer energy of both ions. The spectral weight of the Cr 3d state is completely proportional to the spin concentration x irrespective of the carrier concentration y, indicating that the spin density can be controlled by x as desired. In contrast, the spectral weight of the Ti 3d state is not proportional to y, depending on the amount of Cr doping.     

Three Dimensionality and Orbital Characters of the Fermi Surface in (Tl,Rb)_{y}Fe_{2-x}Se_{2}

We report a comprehensive angle-resolved photoemission spectroscopy study of the tridimensional electronic bands in the recently discovered Fe selenide superconductor (Tl,Rb)_{y}Fe_{2-x}Se_{2} (T_{c}=32 K). We determined the orbital characters and the k_{z} dependence of the low energy electronic structure by tuning the polarization and the energy of the incident photons. We observed a small 3D electron Fermi surface pocket near the Brillouin zone center and a 2D like electron Fermi surface pocket near the zone boundary. The photon energy dependence, the polarization analysis and the local-density approximation calculations suggest a significant contribution from the Se 4p_{z} and Fe 3d_{xy} orbitals to the small electron pocket. We argue that the emergence of Se 4p_{z} states might be the cause of the different magnetic properties between Fe chalcogenides and Fe pnictides.     

Novel orientational ordering and reentrant metallicity in K(x)C(60) monolayers for 3 < or = x < or = 5

STM studies on K(x)C(60) monolayers reveal new behavior over a wide range of the phase diagram. As x increases from 3 to 5 K(x)C(60) monolayers undergo metal-insulator-metal reentrant phase transitions and exhibit a variety of novel orientational orderings, including a complex 7-molecule, pinwheel-like structure. The proposed driving mechanism for the orientational ordering is the lowering of electron kinetic energy by maximizing the overlap of neighboring molecular orbitals. In insulating (metallic) K(x)C(60) this gives rise to orbital versions of the superexchange (double-exchange) interaction.     

Quasi-one-dimensional magnetism driven by unusual orbital ordering in CuSb2O6

Essentially all undoped cuprates exhibit a quasiplanar, fourfold Cu-O coordination responsible for the magnetically active antibonding 3d(x(2)-y(2)) like state. Here, we present an electronic structure study for CuSb(2)O(6) that reveals, in contrast, a half-filled 3d(3z(2)-r(2)) orbital. This hitherto unobserved ground state originates from a competition of in- and out-of-plaquette orbitals where the strong Coulomb repulsion drives the surprising and unique orbital ordering. This, in turn, gives rise to an unexpected quasi-one-dimensional magnetic behavior. Our results provide a consistent explanation of recent thermodynamical and neutron diffraction measurements.     

Orbital fluctuations in the different phases of LaVO(3) and YVO(3)

We investigate the importance of quantum orbital fluctuations in the orthorhombic and monoclinic phases of the Mott insulators LaVO(3) and YVO(3). First, we construct ab initio material-specific t(2g) Hubbard models. Then, by using dynamical mean-field theory, we calculate the spectral matrix as a function of temperature. Our Hubbard bands and Mott gaps are in very good agreement with spectroscopy. We show that in orthorhombic LaVO(3), quantum orbital fluctuations are strong and that they are suppressed only in the monoclinic 140 K phase. In YVO(3)the suppression happens already at 300 K. We show that Jahn-Teller and GdFeO3-type distortions are both crucial in determining the type of orbital and magnetic order in the low temperature phases.     

Systematic (63)Cu NQR and (89)Y NMR study of spin dynamics in Y(1-z)Ca(z)Ba(2)Cu(3)O(y) across the superconductor-insulator boundary

We demonstrate that the spin dynamics in underdoped Y(1-z)Ca(z)Ba(2)Cu(3)O(y) for y approximately equal to 6.0 exhibit qualitatively the same behavior to underdoped La(2-x)Sr(x)CuO(4) for an equal amount of hole concentration p = z/2 = x< or =0.11. However, a spin gap appears as more holes are doped into the CuO(2) plane by increasing the oxygen concentration to y approximately equal to 6.5 for a fixed value of Ca concentration z. Our results also suggest that Ca doping causes disorder effects that enhance the low frequency spin fluctuations.     

Critical behavior of metal-insulator transition in La1-(x)Sr(x)VO3

Critical behavior of the metal-insulator transition (MIT) coupled with spin/orbital correlations has been investigated for single crystals of La1-(x)Sr(x)VO3. In the paramagnetic (PM) metal phase (x > 0.260), the precursor to the MIT manifests itself as an enhancement of carrier effective mass. In the antiferromagnetic (AF) metal phase (0.178 < or = x < or = 0.260), the carrier density decreases and the correlation of the orbital seems to evolve towards the MIT (x = 0.178). In the AF insulating phase (x < 0.178), the distinct first-order structural phase transition occurs with the decrease of temperature, perhaps concomitantly with the orbital ordering.     

Photoinduced magnetization in the organic-based magnet Mn(TCNE)(x)* y(CH2Cl2)

Photoinduced magnetization in a magnet based on organic species is reported for the first time. Upon optical excitation in the blue region of spectrum, Mn(tetracyanoethylene)(x)*y(CH2Cl2) (x approximately 2, y is approximately 0.8) exhibits increased magnetic susceptibility at temperatures as high as 75 K, accompanied with photoinduced absorption in the visible and infrared spectral regions. These effects are partially reversible by lower energy visible light and fully reversible by thermal treatment. The results suggest trapping of the photoexcited charge in a metastable state with enhanced exchange interaction.     

Field-induced ferromagnetic metallic state of bilayer manganite (La0.4Pr0.6)1.2Sr1.8Mn2O7: a polarized neutron diffraction study

Unpolarized and polarized neutron diffraction measurements have been carried out on the bilayer manganite (La0.4Pr0.6)1.2Sr1.8Mn2O7 which undergoes simultaneous semiconductor-metal paraferromagnetic transitions under magnetic field. Maximum entropy magnetization density reconstruction and multipole refinement on flipping ratios evidence the existence of two distinct field-induced states. The field-induced ferromagnetic state where the field is parallel to the c axis is characterized by the presence of magnetic moment on the Sr site of 0.48(2)mu(B), due to the Pr substitution. It also shows a high population of the d3(z(2)-r(2)) orbitals of Mn3+. For the field-induced state where the field is parallel to the a or b axes no magnetization density was found at the Sr site and the dx(2)(-y(2)) orbital is slightly more populated than the d3(z(2)-r(2)) one.     

Crystal-field level inversion in lightly Mn-doped Sr3Ru2O7

Sr3(Ru(1-x)Mnx)2O7, in which 4d-Ru is substituted by the more localized 3d-Mn, is studied by x-ray dichroism and spin-resolved density functional theory. We find that Mn impurities do not exhibit the same 4+ valence of Ru, but act as 3+ acceptors; the extra eg electron occupies the in-plane 3d(x2-y2) orbital instead of the expected out-of-plane 3d(3z2-r2). We propose that the 3d-4d interplay, via the ligand oxygen orbitals, is responsible for this crystal-field level inversion and the material's transition to an antiferromagnetic, possibly orbitally ordered, low-temperature state.     

Bonding, backbonding, and spin-polarized molecular orbitals: basis for magnetism and semiconducting transport in V[TCNE]x approximately 2

X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (MCD) at the V L{2,3} and C and N K edges reveal bonding and backbonding interactions in films of the 400 K magnetic semiconductor V[TCNE]x approximately 2. In V spectra, d{xy}-like orbitals are modeled assuming V2+ in an octahedral ligand field, while d{z{2}} and d{x{2}-y{2}} orbitals involved in strong covalent sigma bonding cannot be modeled by atomic calculations. C and N MCD, and differences in XAS from neutral TCNE molecules, reveal spin-polarized molecular orbitals in V[TCNE]x approximately 2 associated with weaker pi bonding interactions that yield its novel properties.     

Pressure-induced colossal piezoresistance effect and the collapse of the polaronic state in the bilayer manganite (La(0.4)Pr(0.6))(1.2)Sr(1.8)Mn2O7

We have investigated the effect of hydrostatic pressure as a function of temperature on the resistivity of a single crystal of the bilayer manganite (La(0.4)Pr(0.6))(1.2)Sr(1.8)Mn(2)O(7). Whereas a strong insulating behaviour is observed at all temperatures at ambient pressure, a clear transition into a metallic-like behaviour is induced when the sample is subjected to a pressure (P) of ~1.0 GPa at T < 70 K. A huge negative piezoresistance ~10(6) in the low temperature region at moderate pressures is observed. When the pressure is increased further (5.5 GPa), the high temperature polaronic state disappears and a metallic behaviour is observed. The insulator to metal transition temperature exponentially increases with pressure and the distinct peak in the resistivity that is observed at 1.0 GPa almost vanishes for P > 7.0 GPa. A modification in the orbital occupation of the e(g) electron between 3d(x(2)-y(2)) and 3d(z(2)-r(2)) states, as proposed earlier, leading to a ferromagnetic double-exchange phenomenon, can qualitatively account for our data.     

The superconducting transition temperatures of Fe(1+x)Se(1-y), Fe(1+x)Se(1-y)Te(y) and (K/Rb/Cs)(z)Fe(2-x)Se2

In a recent contribution to this journal, it was shown that the transition temperatures of optimal high-T(C) compounds obey the algebraic relation T(C0) = k(-1)(B)/?ζ, where ? is related to the mean spacing between interacting charges in the layers, ζ is the distance between interacting electronic layers, β is a universal constant and k(B) is Boltzmann's constant. The equation was derived assuming pairing based on interlayer Coulomb interactions between physically separated charges. This theory was initially validated for 31 compounds from five different high-T(C) families (within an accuracy of ±1.37 K). Herein we report the addition of Fe(1+x)Se(1-y) and Fe(1+x)Se(1-y)Te(y) (both optimized under pressure) and A(z)Fe(2-x)Se(2) (for A = K, Rb or Cs) to the growing list of Coulomb-mediated superconducting compounds in which T(C0) is determined by the above equation. Doping in these materials is accomplished through the introduction of excess Fe and/or Se deficiency, or a combination of alkali metal and Fe vacancies. Consequently, a very small number of vacancies or interstitials can induce a superconducting state with a substantial transition temperature. The confirmation of the above equation for these Se-based Fe chalcogenides increases to six the number of superconducting families for which the transition temperature can be accurately predicted.     

Angle-resolved photoemission study of the cobalt oxide superconductor Na(x)CoO(2) x yH(2)O: observation of the Fermi surface

The cobalt oxide superconductor Na(x)CoO(2) x yH(2)O is studied by angle-resolved photoemission spectroscopy. We report the Fermi surface (FS) topology and electronic structure near the Fermi level (E(F)) in the normal state of Na(x)CoO(2) x yH(2)O. Our result indicates the presence of the hexagonal FS centered at the Gamma point, while the small pocket FSs along Gamma-K direction are absent, similar to Na(x)CoO(2). The top of the e(g)(') band, which is expected in band calculations to form the small pocket FSs, extends to within approximately 30 meV below E(F), closer to E(F) than in Na(x)CoO(2). We discuss its possible role in superconductivity, comparing with other experimental and theoretical results.     

Theory of the angular distribution of molecular orbitalK x rays seen in heavy-ion-atom collisions

Dynamical calculations of angular distributions and intensities of two-collision 1s σ molecular orbital x rays in 12–90-MeV Ni + Ni collisions are reported. The Coriolis and spin-orbit coupling between 2pσ and 2pπ and the 3pσ and 3pπ molecular orbitals is included. Due to Coriolis coupling, the molecular wavefunctions and therefore the transition dipoles do not follow the rotation of the internuclear axis in collisions with small impact parameters, but remain approximately fixed in direction. Consequently one can predict the symmetry relations between the laboratoryx, y, andz components of the molecular orbital intensity and therefore the anisotropy of the radiation seen at energies near the united atomK α x-ray line. These relations are used to predict anisotropies of molecular orbital radiation in encounters with large united atom atomic numbers,Z ₁ +Z ₂>137. For Ni + Ni encounters, a lower population of the 2pπ and 3pπ orbitals than the 2pσ and 3pσ orbitals is needed to reproduce the observed anisotropies.