Doping Dependent Changes in Nitrogen 2pp States in the Diluted Magnetic Semiconductor Ga1−x_{1-x}Crx_{x}N

We study the electronic structure of the recently discovered diluted magnetic semiconductor Ga$_{1-x}$Cr$_{x}$N ($x$ = 0.01-0.10). A systematic study of the changes in the $occupied$ and $unoccupied$ ligand (N) partial density of states (DOS) of the host lattice is carried out using N 1$s$ soft x-ray emission and absorption spectroscopy, respectively. X-ray absorption measurements confirm the wurtzite N 2$p$ DOS and substitutional doping of Cr into Ga-sites. Coupled changes in the $occupied$ and $unoccupied$ N 2$p$ character DOS of Ga$_{1-x}$Cr$_{x}$N identify states responsible for ferromagnetism consistent with band structure calculations.Comment: 5 pages, 4 figures, submitted to Phys. Rev.

Direct Observation of Site-specific Valence Electronic Structure at Interface: SiO2/Si Interface

Atom specific valence electronic structures at interface are elucidated successfully using soft x-ray absorption and emission spectroscopy. In order to demonstrate the versatility of this method, we investigated SiO2/Si interface as a prototype and directly observed valence electronic states projected at the particular atoms of the SiO2/Si interface; local electronic structure strongly depends on the chemical states of each atom. In addition we compared the experimental results with first-principle calculations, which quantitatively revealed the interfacial properties in atomic-scale.Comment: 4 pages, 3 figure

Immittance Matching for Multi-dimensional Open-system Photonic Crystals

An electromagnetic (EM) Bloch wave propagating in a photonic crystal (PC) is characterized by the immittance (impedance and admittance) of the wave. The immittance is used to investigate transmission and reflection at a surface or an interface of the PC. In particular, the general properties of immittance are useful for clarifying the wave propagation characteristics. We give a general proof that the immittance of EM Bloch waves on a plane in infinite one- and two-dimensional (2D) PCs is real when the plane is a reflection plane of the PC and the Bloch wavevector is perpendicular to the plane. We also show that the pure-real feature of immittance on a reflection plane for an infinite three-dimensional PC is good approximation based on the numerical calculations. The analytical proof indicates that the method used for immittance matching is extremely simplified since only the real part of the immittance function is needed for analysis without numerical verification. As an application of the proof, we describe a method based on immittance matching for qualitatively evaluating the reflection at the surface of a semi-infinite 2D PC, at the interface between a semi-infinite slab waveguide (WG) and a semi-infinite 2D PC line-defect WG, and at the interface between a semi-infinite channel WG and a semi-infinite 2D PC slab line-defect WG.Comment: 8 pages, 6 figure

X ray emission spectroscopy of bulk liquid water in no man s land

The structure of bulk liquid water was recently probed by x ray scattering below the temperature limit of homogeneous nucleation TH of amp; 8764;232 K [J. A. Sellberg et al., Nature 510, 381 384 2014 ]. Here, we utilize a similar approach to study the structure of bulk liquid water below TH using oxygen K edge x ray emission spectroscopy XES . Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387 400 2008 ] at higher temperatures, we expected the ratio of the 1b1 amp; 8242; and 1b1 amp; 8242; amp; 8242; peaks associated with the lone pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen H bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more importan

Ab initio van der Waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like

The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations using van der Waals (vdW) density-functional theory, i.e. using the new exchange-correlation functionals optPBE-vdW and vdW-DF2. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen-bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen-oxygen pair-correlation function (PCF), indicating loss of structure in the outer solvation shells. In combination with softer non-local correlation terms, as in the new parameterization of vdW-DF, inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O-O PCF shows some resemblance with experiment for high-density water (A. K. Soper and M. A. Ricci, Phys. Rev. Lett., 84:2881, 2000), but not directly with experiment for ambient water. However, an O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from experiment on low-density liquid water reproduces near-quantitatively the experimental O-O PCF for ambient water, indicating consistency with a two-liquid model with fluctuations between high- and low-density regions

Probing the Hofmeister Effect with Ultrafast Core Hole Spectroscopy

In the current work, X-ray emission spectra of aqueous solutions of different inorganic salts within the Hofmeister series are presented. The results reflect the direct interaction of the ions with the water molecules and therefore, reveal general properties of the salt-water interactions. Within the experimental precision a significant effect of the ions on the water structure has been observed but no ordering according to the structure maker/structure breaker concept could be mirrored in the results indicating that the Hofmeister effect-if existent-may be caused by more complex interactions

Chemical Modification of Graphene Oxide by Nitrogenation: An X-ray Absorption and EmissionSpectroscopy Study

Nitrogen-doped graphene oxides (GO:Nx) were synthesized by a partial reduction of graphene oxide (GO) using urea [CO(NH2)2]. Their electronic/bonding structures were investigated using X-ray absorption near-edge structure (XANES), valence-band photoemission spectroscopy (VB-PES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). During GO:Nx synthesis, different nitrogen-bonding species, such as pyrrolic/graphitic-nitrogen, were formed by replacing of oxygen-containing functional groups. At lower N-content (2.7 at%), pyrrolic-N, owing to surface and subsurface diffusion of C, N and NH is deduced from various X-ray spectroscopies. In contrast, at higher N-content (5.0 at%) graphitic nitrogen was formed in which each N-atom trigonally bonds to three distinct sp2-hybridized carbons with substitution of the N-atoms for C atoms in the graphite layer. Upon nitrogen substitution, the total density of state close to Fermi level is increased to raise the valence-band maximum, as revealed by VB-PES spectra, indicating an electron donation from nitrogen, molecular bonding C/N/O coordination or/and lattice structure reorganization in GO:Nx. The well-ordered chemical environments induced by nitrogen dopant are revealed by XANES and RIXS measurements