Multiplet resonance lifetimes in resonant inelastic X-ray scattering involving shallow core levels

Resonant inelastic X-ray scattering (RIXS) spectra of model copper- and nickel-based transition metal oxides are measured over a wide range of energies near the M-edge (h$\nu$=60-80eV) to better understand the properties of resonant scattering involving shallow core levels. Standard multiplet RIXS calculations are found to deviate significantly from the observed spectra. However, by incorporating the self consistently calculated decay lifetime for each intermediate resonance state within a given resonance edge, we obtain dramatically improved agreement between data and theory. Our results suggest that these textured lifetime corrections can enable a quantitative correspondence between first principles predictions and RIXS data on model multiplet systems. This accurate model is also used to analyze resonant elastic scattering, which displays the elastic Fano effect and provides a rough upper bound for the core hole shake-up response time.Comment: 6 pages, 3 figure

Disorder enabled band structure engineering of a topological insulator surface

Three dimensional topological insulators are bulk insulators with $\mathbf{Z}_2$ topological electronic order that gives rise to conducting light-like surface states. These surface electrons are exceptionally resistant to localization by non-magnetic disorder, and have been adopted as the basis for a wide range of proposals to achieve new quasiparticle species and device functionality. Recent studies have yielded a surprise by showing that in spite of resisting localization, topological insulator surface electrons can be reshaped by defects into distinctive resonance states. Here we use numerical simulations and scanning tunneling microscopy data to show that these resonance states have significance well beyond the localized regime usually associated with impurity bands. At native densities in the model Bi$_2$X$_3$ (X=Bi, Te) compounds, defect resonance states are predicted to generate a new quantum basis for an emergent electron gas that supports diffusive electrical transport

Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries.

A sodium-ion battery (SIB) solution is attractive for grid-scale electrical energy storage. Low-cost hexacyanometalate is a promising electrode material for SIBs because of its easy synthesis and open framework. Most hexacyanometalate-based SIBs work with aqueous electrolyte, and interstitial water in the material has been found to strongly affect the electrochemical profile, but the mechanism remains elusive. Here we provide a comparative study of the transition-metal redox in hexacyanometalate electrodes with and without interstitial water based on soft X-ray absorption spectroscopy and theoretical calculations. We found distinct transition-metal redox sequences in hydrated and anhydrated NaxMnFe(CN)6·zH2O. The Fe and Mn redox in hydrated electrodes are separated and are at different potentials, leading to two voltage plateaus. On the contrary, mixed Fe and Mn redox in the same potential range is found in the anhydrated system. This work reveals for the first time how transition-metal redox in batteries is strongly affected by interstitial molecules that are seemingly spectators. The results suggest a fundamental mechanism based on three competing factors that determine the transition-metal redox potentials. Because most hexacyanometalate electrodes contain water, this work directly reveals the mechanism of how interstitial molecules could define the electrochemical profile, especially for electrodes based on transition-metal redox with well-defined spin states

Electron dynamics in topological insulator based semiconductor-metal interfaces (topological p-n interface based on Bi2Se3 class)

Single-Dirac-cone topological insulators (TI) are the first experimentally discovered class of three dimensional topologically ordered electronic systems, and feature robust, massless spin-helical conducting surface states that appear at any interface between a topological insulator and normal matter that lacks the topological insulator ordering. This topologically defined surface environment has been theoretically identified as a promising platform for observing a wide range of new physical phenomena, and possesses ideal properties for advanced electronics such as spin-polarized conductivity and suppressed scattering. A key missing step in enabling these applications is to understand how topologically ordered electrons respond to the interfaces and surface structures that constitute a device. Here we explore this question by using the surface deposition of cathode (Cu/In/Fe) and anode materials (NO$_2$) and control of bulk doping in Bi$_2$Se$_3$ from P-type to N-type charge transport regimes to generate a range of topological insulator interface scenarios that are fundamental to device development. The interplay of conventional semiconductor junction physics and three dimensional topological electronic order is observed to generate novel junction behaviors that go beyond the doped-insulator paradigm of conventional semiconductor devices and greatly alter the known spin-orbit interface phenomenon of Rashba splitting. Our measurements for the first time reveal new classes of diode-like configurations that can create a gap in the interface electron density near a topological Dirac point and systematically modify the topological surface state Dirac velocity, allowing far reaching control of spin-textured helical Dirac electrons inside the interface and creating advantages for TI superconductors as a Majorana fermion platform over spin-orbit semiconductors.Comment: 14 pages, 4 Figure