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We have studied the electronic structure of bulk single crystals and epitaxial films of magnetite Fe$_3$O$_4$. Fe $2p$ core-level spectra show clear differences between hard x-ray (HAX-) and soft x-ray (SX-) photoemission spectroscopy (PES), indicative of surface effects. The bulk-sensitive spectra exhibit temperature ($T$)-dependent charge excitations across the Verwey transition at $T_V$=122 K, which is missing in the surface-sensitive spectra. An extended impurity Anderson model full-multiplet analysis reveals roles of the three distinct Fe-species (A-Fe$^{3+}$, B-Fe$^{2+}$, B-Fe$^{3+}$) below $T_V$ for the Fe $2p$ spectra, and its $T-$dependent evolution. The Fe $2p$ HAXPES spectra show a clear magnetic circular dichroism (MCD) in the metallic phase of magnetized 100-nm-thick films. The model calculations also reproduce the MCD and identify the magnetically distinct sites associated with the charge excitations. Valence band HAXPES shows finite density of states at $E_F$ for the polaronic metal with remnant order above $T_V$, and a clear gap formation below $T_V$. The results indicate that the Verwey transition is driven by changes in the strongly correlated and magnetically active B-Fe$^{2+}$ and B-Fe$^{3+}$ electronic states, consistent with resistivity and bulk-sensitive optical spectra., Comment: 5 pages, 4 figures Accepted in Physical Review Letters

The electronic structure of doped Mn in (Ga,Mn)As is studied by resonant inelastic X-ray scattering (RIXS). From configuration-interaction cluster-model calculations, the line shapes of the Mn $L_3$ RIXS spectra can be explained by $d$-$d$ excitations from the Mn$^{3+}$ ground state, dominated by charge-transferred states, rather than a Mn$^{2+}$ ground state. Unlike archetypical $d$-$d$ excitation, the peak widths are broader than the experimental energy resolution. We attribute the broadening to a finite lifetime of the $d$-$d$ excitations, which decay rapidly to electron-hole pairs in the host valence and conduction bands through hybridization of the Mn $3d$ orbital with the ligand band., Comment: 5 pages, 3 figures

Phase-shift differences and amplitude ratios of the outgoing $s$ and $d$ continuum wave packets generated by two-photon ionization of helium atoms are determined from the photoelectron angular distributions obtained using velocity map imaging. Helium atoms are ionized with ultrashort extreme-ultraviolet free-electron laser pulses with a photon energy of 20.3, 21.3, 23.0, and 24.3 eV, produced by the SPring-8 Compact SASE Source test accelerator. The measured values of the phase-shift differences are distinct from scattering phase-shift differences when the photon energy is tuned to an excited level or Rydberg manifold. The difference stems from the competition between resonant and non-resonant paths in two-photon ionization by ultrashort pulses. Since the competition can be controlled in principle by the pulse shape, the present results illustrate a new way to tailor the continuum wave packet., Comment: 5 pages, 1 table, 3 figures

We report on the electronic structure of the perovskite oxide CaCrO3 using valence-band, core-level, and Cr 2p - 3d resonant photoemission spectroscopy (PES). Despite its antiferromagnetic order, a clear Fermi edge characteristic of a metal with dominant Cr 3d character is observed in the valence band spectrum. The Cr 3d single particle density of states are spread over 2 eV, with the photoemission spectral weight distributed in two peaks centered at ~ 1.2 eV and 0.2 eV below EF, suggestive of the coherent and incoherent states resulting from strong electron-electron correlations. Resonant PES across the Cr 2p - 3d threshold identifies a 'two-hole' correlation satellite and yields an on-site Coulomb energy U ~4.8 eV. The metallic DOS at EF is also reflected through the presence of a well-screened feature at low binding energy side of the Cr 2p core-level spectrum. X-ray absorption spectroscopy (XAS) at Cr L3,2 and O K edges exhibit small temperature dependent changes that point towards a small change in Cr-O hybridization. The multiplet splitting in Cr 2p core level spectrum as well as the spectral shape of the Cr XAS can be reproduced using cluster model calculations which favour a negative value for charge transfer energy between the Cr 3d and O 2p states. The overall results indicate that CaCrO3 is a strongly hybridized antiferromagnetic metal, lying in the regime intermediate to Mott-Hubbard and charge-transfer systems.

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co:TiO2 anatase films using soft and hard x-ray photoemission spectroscopy with probe sensitivities of ~1 nm and ~10 nm, respectively. We obtain direct evidence of metallic Ti$^{3+}$ states in the bulk, which get suppressed to give a surface semiconductor, thus indicating a surface-bulk dichotomy. X-ray absorption and high-sensitivity resonant photoemission spectroscopy reveal Ti$^{3+}$ electrons at the Fermi level (E$_F$) and high-spin Co$^{2+}$ electrons occurring away from E$_F$. The results show the importance of the charge neutrality condition: Co$^{2+}$ + V$_{O}$$^{2-}$ + 2Ti$^{4+}$ $\leftrightarrow$ Co$^{2+}$ + 2Ti$^{3+}$ (V$_O$ is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals., Comment: 4 pages, 4 figures

We investigate the electronic structure of Chromium Nitride (CrN) across the first-order magneto-structural transition at T_N ~ 286 K. Resonant photoemission spectroscopy shows a gap in the 3d partial density of states at the Fermi level and an On-site Coulomb energy U ~ 4.5 eV, indicating strong electron-electron correlations. Bulk-sensitive high resolution (6 meV) laser photoemission reveals a clear Fermi edge indicating an antiferromagnetic metal below T_N. Hard x-ray Cr 2p core-level spectra show T-dependent changes across T_N which originate from screening due to coherent states as substantiated by cluster model calculations using the experimentally observed U. The electrical resistivity confirms an insulator above T_N (E_g ~ 70 meV) which becomes a disordered metal below T_N. The results indicate CrN transforms from a correlated insulator to an antiferromagnetic metal, coupled to the magneto-structural transition., Comment: Submitted to Physical Review Letters (February 2010) 11 pages, 3 figures in the main text, 1 Supplementary Information

Epitaxial ultrathin Fe films on fcc Cu(001) exhibit a spin spiral (SS), in contrast to the ferromagnetism of bulk bcc Fe. We study the in-plane and out-of-plane Fermi surfaces (FSs) of the SS in 8 monolayer Fe/Cu(001) films using energy dependent soft x-ray momentum-resolved photoemission spectroscopy. We show that the SS originates in nested regions confined to out-of-plane FSs, which are drastically modified compared to in-plane FSs. From precise reciprocal space maps in successive zones, we obtain the associated real space compressive strain of 1.5+-0.5% along c-axis. An autocorrelation analysis quantifies the incommensurate ordering vector q=(2pi/a)(0,0,~0.86), favoring a SS and consistent with magneto-optic Kerr effect experiments. The results reveal the importance of in-plane and out-of-plane FS mapping for ultrathin films., Comment: 4 pages, 3 figures

Soft-x-ray photoemission and absorption spectroscopies are employed to investigate the electronic structures of Sr_{1-x}Rh_{2}O_{4}. Similarly to the layered cobaltates such as Na_{1-x}CoO_{2}, a valence-band satellite feature (VBS) occurs at higher binding energy to the O 2p band. We find that the VBS resonates at the O 1s edge. Additionally, core absorption shows clear x dependence in the O 1s edge rather than in the Rh 3p edge. These results indicate that the holes in the initial state mainly have O 2p character presumably due to d-p rehybridizations affected by Sr^{2+} vacancy potentials. The resultant inhomogenous charge texture may have impact on the TE transport properties at low x.

We report the three-dimensional (3-D) momentum-resolved soft x-ray photoemission spectroscopy of the Fermi liquid LaNiO$_3$. The out-of-plane and in-plane cuts of the 3-D electron- and hole-Fermi surfaces (FSs) are observed by energy- and angle- dependent photoemission measurements. The energy bands forming the electron FS suggest an $\omega^2$ dependence of the imaginary part of the self-energy and a `correlation kink' at an energy scale of 0.25 eV. In contrast, the bands which form nesting character hole FSs do not show kinks and match local density approximation calculations. The results indicate a momentum-dependent mass renormalization, leading to electron-hole asymmetry in strongly correlated LaNiO$_3$., Comment: 6 pages, 5 figures, Physical Review B, to be published

The Magneli phase Ti4O7 exhibits two sharp jumps in resistivity with coupled structural transitions as a function of temperature at Tc1=142 K and Tc2=154 K. We have studied electronic structure changes across the two transitions using 7 eV laser, soft x-ray and hard x-ray (HX) photoemission spectroscopy (PES). Ti 2p-3d resonant PES and HX-PES show a clear metallic Fermi-edge and mixed valency above Tc2. The low temperature phase below Tc1 shows a clear insulating gap of 100 meV. The intermediate phase between Tc1 and Tc2 indicates a pseudogap coexisting with remnant coherent states. HX-PES and complementary calculations have confirmed the coherent screening in the strongly correlated intermediate phase. The results suggest existence of a highly anomalous state sandwiched between the mixed-valent Fermi liquid and charge ordered Mott-insulating phase in Ti4O7., Comment: 4 pages, 3 figures

Hard x-ray photoemission and optical spectroscopies have been performed on YbS and Yb metal to determine the precise $f$-electron occupation. A comparison of the photoemission spectra with the energy loss functions in bulk and surface, obtained from optical reflectivity, enables us to distinguish between the energy loss satellite of Yb$^{2+}$ peak and Yb$^{3+}$ multiplet. The results clearly indicate a purely divalent Yb state except for the surface of YbS. We demonstrate that the present method is highly reliable in identifying the electronic structure and the mean valence in $f$-electron systems.

High energy resolution photoelectron spectroscopy of conduction electrons in the vicinity of the Fermi-edge in Al and Au at the excitation energy of 880 and 7940 eV was carried out using synchrotron radiation. For the excitation energy of 7940 eV, the observed Fermi energy of Al shows a remarkable shift to higher binding energy as compared with that of Au, with accompanying broadening. This is due to the recoil effect of the emitted photoelectrons. The observed spectra are well reproduced by a simple model of Bloch electrons based on the isotropic Debye model., Comment: 5 pages, 2 figures

Resonant photoemission at the Ti 2p and O 1s edges on a Nb-doped SrTiO3 thin film revealed that the coherent state (CS) at the Fermi level (EF) had mainly Ti 3d character whereas the incoherent in-gap state (IGS) positioned ~1.5 eV below EF had mixed character of Ti 3d and O 2p states. This indicates that the IGS is formed by a spectral-weight transfer from the CS and subsequent spectral-weight redistribution through d-p hybridization. We discuss the evolution of the excitation spectrum with 3d band filling and rationalize the IGS through a mechanism similar to that proposed by Haldane and Anderson.

We have re-examined the valence-band (VB) and core-level electronic structure of NiO by means of hard and soft x-ray photoemission spectroscopy (PES). The spectral weight of the lowest energy state found to be enhanced in the bulk sensitive Ni 2p core-level PES. A configuration-interaction model including the bound state screening has shown significant agreement with the core-level spectra, and the off and on-resonance VB spectra. These results identify the lowest energy state in core-level and VB-PES as the Zhang-Rice doublet bound state, consistent with the spin-fermion model and recent ab initio calculation with dynamical mean-field theory (LDA + DMFT)., Comment: 4 pages, 3 figures

The temperature ($T$) dependent metal-insulator transition (MIT) in VO$_2$ is investigated using bulk sensitive hard x-ray ($\sim$ 8 keV) valence band, core level, and V 2$p-3d$ resonant photoemission spectroscopy (PES). The valence band and core level spectra are compared with full-multiplet cluster model calculations including a coherent screening channel. Across the MIT, V 3$d$ spectral weight transfer from the coherent ($d^1\underbar{\it {C}}$ final) states at Fermi level to the incoherent ($d^{0}+d^1\underbar{\it {L}}$ final) states, corresponding to the lower Hubbard band, lead to gap-formation. The spectral shape changes in V 1$s$ and V 2$p$ core levels as well as the valence band are nicely reproduced from a cluster model calculations, providing electronic structure parameters. Resonant-PES finds that the $d^1\underbar{\it{L}}$ states resonate across the V 2$p-3d$ threshold in addition to the $d^{0}$ and $d^1\underbar{\it {C}}$ states. The results support a Mott-Hubbard transition picture for the first order MIT in VO$_2$., Comment: 6 pages, 3 figures. to be published in Phys. Rev. B

We investigate the electronic structure of high-quality single-crystal LaNiO$_3$ (LNO) thin films using in situ photoemission spectroscopy (PES). The in situ high-resolution soft x-ray PES measurements on epitaxial thin films reveal the intrinsic electronic structure of LNO. We find a new sharp feature in the PES spectra crossing the Fermi level, which is derived from the correlated Ni 3$d$ $e_g$ electrons. This feature shows significant enhancement of spectral weight with decreasing temperature. From a detailed analysis of resistivity data, the enhancement of spectral weight is attributed to increasing electron correlations due to antiferromagnetic fluctuations., Comment: 4 pages, 4 figures. submitted to Phys. Rev. B

Semiconducting skutterudite CeFe$_4$P$_{12}$ is investigated by synchrotron x-ray photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). Ce 3$d$ core-level PES and 3$d-4f$ XAS, in combination with single impurity Anderson model (SIAM) calculations, confirm features due to $f^0$, $f^1$ and $f^2$ configurations. The Ce 4$f$ density of states (DOS) indicates absence of a Kondo resonance at Fermi level, but can still be explained by SIAM with a small gap in non-$f$ DOS. While Ce 4$f$ partial DOS from band structure calculations are also consistent with the main Ce 4$f$ DOS, the importance of SIAM for core and valence spectra indicates Kondo semiconducting mixed valence for CeFe$_4$P$_{12}$, derived from strong hybridization between non-$f$ conduction and Ce 4$f$ DOS., Comment: 4pages, 4figures

We study the mixed valence transition ($T$$_{v}$ $\sim$80 K) in EuNi$_{2}$(Si$_{0.2}$Ge$_{0.8}$)$_{2}$ using Eu 3$d-4f$ X-ray absorption spectroscopy (XAS) and resonant photoemission spectroscopy (RESPES). The Eu$^{2+}$ and Eu$^{3+}$ main peaks show a giant resonance and the spectral features match very well with atomic multiplet calculations. The spectra show dramatic temperature ($T$)-dependent changes over large energies ($\sim$10 eV) in RESPES and XAS. The observed non-integral mean valencies of $\sim$2.35 $\pm$ 0.03 ($T$ = 120 K) and $\sim$2.70 $\pm$ 0.03 ($T$ = 40 K) indicate homogeneous mixed valence above and below $T$$_{v}$. The redistribution between Eu$^{2+}$$4f^7$+$[spd]^0$ and Eu$^{3+}$$4f^6$+$[spd]^1$ states is attributed to a hybridization change coupled to a Kondo-like volume collapse., Comment: 4 pages, 3 figures