1. Photon-in/Photon-out Soft-X-Ray Spectroscopy Soft-X-Ray Absorption (XAS); Soft-X-Ray Emission (XES) Resonant Inelastic Soft-X-Ray Scattering (RIXS) Jinghua Guo (ALS) (a)(b) XAS,XES: I    3  N G (E )| G,l  1 |r|c l >| 2 XAS and XES features: Elemental selectivity Chemical sensitivity Bulk sensitivity Primary excitation: < 10 -15 s De-excitation: 10 -15 s

2. VUV energy range: 30 to 250 eV Soft x-ray energy range: 250 to 2000 eV K edge 530 eV 3d3d E Fermi E 3p3p 3s3s 2p 1s1s 2s2s M 2,3 edges (28-77 eV) L 2,3 edges (400-1050 eV) 2p2p 3d TM Oxygen 4sp4sp 3d Rare Earths 5d 4d O 4,5 edges N 4,5 edges (100-250 eV) 5d5d 4f4f M 4,5 edges (830-1580 eV) M 1 edges (80-150 eV) The Working Range of Soft-X-Ray Beamline 7.0.1 energy range: 80 to 1100 eV 5 meV: R = 500 @ 2.5 eV R = 10,000 @ 50 eV R = 200,000 @ 1000 eV

3. Resonant Inelastic Soft-X-Ray Scattering RIXS features: Site selectivity Energy conservation Symmetry selection (parity conservation) Dynamics Chemical bond probing RIXS: Resonant Inelastic X-ray Scattering Kramers-Heisenberg formula: Appl. to d and f systems, see e.g.: S. Butorin, et al., Phys. Rev. Lett., 77, 574 (1996) h  ´= h  -  E dd p-core level EFEF d,f hh Photon in Photon out Two-photon, core-edge resonance enhanced valence band excitation F(  ´  =    g  f  ´  f m E g +  - E m - i  m 2

4. Low Energy High Resolution RIXS at Cu M-Edge Kuiper et al., PRL 80, 5204 (1998) Sr 2 CuO 2 Cl 2  Core-hole lifetime does not limit the resolution of RIXS  dd-excitations resolved  Magnon-excitation (spin flip) resolved dd Indirect probing of magnon (spin-flip) excitation  E = 200 meV at 30  m slit) Spin-flip Chiuzbåian et al., PRL 95, 197402 (2005) SLS experiment NiO Mueller et al., PRB 46, 11069 (1992).

5. Science 2000 High-Temperature Superconductivity (HTS) and Colossal Magnetoresistance (CMR) Orbital degree of freedom correlation and order-disorder transition strong coupling with charge, spin, and lattice dynamics RIXS can be used to determine the energy levels

6. High Resolution Measurements for MnO Ghiringhelli et al. (2005) Resolution: 0.3 eV (FWHM) Resolution: ~ 0.1 eV e Ghiringhelli et al. (2009) Resolution: 1.6 eV (FWHM) Butorin et al. (1996) expt atomic calculation

7. Dispersion (q-dependence) in RIXS of SrCuO 2 spinon pair and holon/antiholon excitation L. Duda (Uppsala Univ.) @SLS spinon pair holon/antiholon calculation courtesy of K.Okada Okayama University

8. RIXS Spectra of YbInCu 4 at Zero or Strong Magnetic Field 40meV ~ kBTKkBTK Singlet bound state Magnetic excited states 4f 14 +4f 13 C k Akio Kotani (3d-edge, 1500 eV)

9. O. Fuchs et al., Phys. Rev. Lett. 100 (2008) 027801. T. Tokushima et al., Chem. Phys. Lett. 460 (2008) 387 J. Forsberg et al., Phys. Rev. B 79 (2009) 132203 XAFS13 (Stanford), July 2006 By courtesy of S. Shin

10. Femtosecond dynamics by detuned RIXS P. Glans et al., Phys. Rev. Lett. 76, 2448 (1996) P. Glans et al., J. Elcetr. Spectr. Rel. Phenom. 82, 3 (1996) * Ground state Core state The resonant excitation O 1s –  u is followed by the ”forbidden”  u – O 1s XES due to dynamical symmetry breaking. Detuning the excitation energy from resonance reduces intensity of ”forbidden” line, indicating restoration of symmetry. P. Skytt, et al., Phys. Rev. Lett., 77, 5035 (1996) A. Cesar, et al, J. Chem. Phys. 107, 2699 (1997) Nordgren et al., JCP 76, 3928 (1982) fast slow O 1s core hole lifetime: < 5 fs (0.15 eV)  g u g u 1u1u 1g1g

11. In-situ Electronic Study in Renewable Energy Scientific Challenges Lithium batteries: higher energy capacity, longer cycle life SOFC: Enrico Traversa (NIMS, Japan) Photocatalytic reaction: Artur Braun (EMPA - Swiss Federal Lab's f. Mater. Testing & Research) Electrochemical reaction: Miquel Salmeron (MSD, MF) Yi Cui, Nature Nanotechnology 3, 31 (2008), Stanford Univ.

12. Probing Charge Transfer (CT) in Photocatalytic Nanomaterials H. Frei (PBD) and J.-H. Guo (ALS) Si Co 3 O 4 Co Co 3 O 4 nanoparticles in nanoporous Silica for Water Oxidation O 2 yield is 1600 times higher for SBA- 15/Co 3 O 4 (35 nm) compared that of bare Co 3 O 4 micron sized particles per weight F. Jiao and H. Frei, Angew. Chem. 121, 1873 (2009)

13. Development of in-situ Cells Co to Ligand transition Co e-e- Liu et al., Nano Lett. (2007) Static Liquid Cell Guo et al., PRL (2002) Guo et al., PRL (2003) Catalytic Reaction Cell Herranz et al., J. Phys. Chem. B. (2009) Oxidized Co foil being reduced under 20 torr H 2 at ~250 °C. Si 3 N 4 (100nm) Cu film (180nm) (WE) Cr (3nm) Pt wire (CE) Ag wire (RE) 2 mM NaHCO 3 Potentiostat X-rays in 1 Fluorescence out Electrochemical Cell Cyclic Voltammetric (CV) curve