Anisotropic valence-->core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]·H2O single crystal: Experimental results and density functional calculations

High resolution x-ray fluorescence spectra have been recorded for emission in different directions from a single crystal of the compound [Rh(en)3][Mn(N)(CN)5]·H2O. The spectra are interpreted by comparison with density functional theory (DFT) electronic structure calculations. The Kbeta[double-prime] line, which is strongly polarized along the Mn–N axis, can be viewed as an N(2s)-->Mn(1s) transition, and the angular dependence is understood within the dipole approximation. The so-called Kbeta2,5 region has numerous contributions but is dominated by Mn(4p) and C(2s)-->Mn(1s) transitions. Transition energy splittings are found in agreement with those of calculated occupied molecular orbitals to within 1 eV. Computed relative transition probabilities reproduce experimentally observed trends

Influence of the core hole on Kß emission following photoionization or orbital electron capture: a comparison using MnO and 55Fe2O3

The Mn K ß fluorescence emission in MnO after photoionization and in "Fe 2 O 3 after radioactive electron capture decay from the K shell have been measured using a crystal array spectrometer with an instrumental energy bandwidth of 0.7 eV (full width at half maximum). Both compounds have a 3d 5 valence electron configuration in the ionic approximation. It is found that the spectral features after K capture in 55 Fe 2 O 3 are shifted in emission energy and are sharper, compared to the spectra following photoionization in MnO, i.e., the spectra exhibit a dependence on the mode of excitation. Crystal-field multiplet calculations including ligand-to- metal charge transfer have been carried out for the 1s intermediate states as well as for the 3p to 1s (K ß) radiative transition. The populated 1s intermediate states after photoionization are found to be spread over several eV. In comparison, only the lowest-lying 1s intermediate states split by the weak (1s,3d) exchange interaction are populated after K capture. It is proposed that the differences in population of the 1s intermediate states together with a term-dependent final-state lifetime broadening can account for the changes in the spectral shapes due to the different modes of excitation

High Resolution K Capture X-ray Fluorescence Spectroscopy: A New Tool for Chemical Characterization

The ability to probe specific chemical sites in complex systems would make X-ray spectroscopy a far more versatile spectroscopic tool. In vibrational and magnetic resonance spectroscopies, isotopic substitution is commonly employed to allow characterization of particular species. Except in a few special cases, such as gas-phase spectra of light elements, isotope effects are too small to be observed in X-ray absorption spectra. An alternative approach is to examine the X-ray emission that results after electron capture by a radioactive isotope.^1,2 Controlled introduction of electron-capture isotopes could result in specific labeling of chemically distinct sites. In this paper, we show that highresolution electron capture fluorescence spectra can be obtained on a reasonable time scale. Chemical shifts in these spectra can be used to identify elemental spin states, oxidation states, and even the types of neighboring atoms. In the electron-capture process an inner shell electron reacts with a nuclear proton to yield a neutron and a neutrino

Hard x-ray photon-in-photon-out spectroscopy with lifetime resolution – of XAS, XES, RIXSS and HERFD

Spectroscopic techniques that aim to resolve the electronic configuration and local coordination of a central atom by detecting inner-shell radiative decays following photoexcitation using hard X-rays are presented. The experimental setup requires an X-ray spectrometer based on perfect crystal Bragg optics. The possibilities arising from non-resonant (X-Ray Emission Spectroscopy - XES) and resonant excitation (Resonant Inelastic X-Ray Scattering Spectroscopy – RIXSS, High-Energy-Resolution Fluorescence Detected (HERFD) XAS) are discussed when the instrumental energy broadenings of the primary (beamline) monochromator and the crystal spectrometer for x-ray emission detection are on the order of the core hole lifetimes of the intermediate and final electronic states. The small energy bandwidth in the emission detection yields line-sharpened absorption features. In transition metal compounds, electron-electron interactions as well as orbital splittings and fractional population can be revealed. Combination with EXAFS spectroscopy enables to extent the k-range beyond unwanted absorption edges in the sample that limit the EXAFS range in conventional absorption spectroscopy

High-resolution Mn K-edge x-ray emission and absorption spectroscopy study of the electronic and local structure of the three different phases in Nd0.5Sr0.5MnO3

Nd0.5Sr0.5MnO3 is particularly representative of mixed-valent manganites since their three characteristic macroscopic phases (charge-ordered insulator, ferromagnetic-metallic, and paramagnetic insulator) appear at different temperatures.We here report a complete x-ray emission and absorption spectroscopy (XES-XAS) study of Nd0.5Sr0.5MnO3 as a function of temperature to investigate the electronic and local structure changes of the Mn atom in these three phases. Compared with the differences in the XES-XAS spectra between Nd0.5Sr0.5MnO3 and the single-valent reference compounds NdMnO3 (Mn3+) and Sr/CaMnO3 (Mn4+), only modest changes have been obtained across the magnetoelectrical transitions. The XES spectra, including both the Mn Kα and Kβ emission lines, have mainly shown a subtle decrease in the local spin density accompanying the passage to the ferromagnetic-metallic phase. For the same phase, the small intensity variations in the pre-edge region of the high-resolution XAS spectra reflect an increase of the p-d mixing. The analysis of these XAS spectra imply a charge segregation between the two different Mn sites far from one electron, being in intermediate valences Mn+3.5±δ/2(δ < 0.2 e−) for all the phases. Our results indicate that the spin, charge, and geometrical structure of the Mn atom hardly change among the three macroscopic phases demonstrating the strong competition between the ferromagnetic conductor and the charge-0rdered insulator behaviors in the manganites

Intrinsic deviations in fluorescence yield detected x ray absorption spectroscopy the case of the transition metal L 2,3 edges

Fluorescence yield FY detected x ray absorption spectra XAS of 3d transition metal ions are calculated from the integrated 2p3d resonant x ray emission spectra. The resulting FY XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY XAS spectrum identifies with the XAS spectrum is disproved. Especially for the early transition metal systems the differences between the FY XAS and XAS are large, due to the opening of inelastic decay channels from selected x ray absorption final states. The theoretical calculations show that the difference between FY detection and XAS is largest for the detection in depolarized geometry. The calculations are compared with experimental spectra for oxides and coordination compounds for Fe2C, Co2C and Ni2C systems. The implications for the sum rules in XAS and magnetic circular dichroism experiments are discusse

Spin-polarized electronic structure of the core-shell ZnO/ZnO:Mn nanowires probed by x-ray absorption and emission spectroscopy

The combination of x-ray spectroscopy methods complemented with theoretical analysis unravels the coexistence of paramagnetic and antiferromagnetic phases in the Zn_0.9Mn_0.1O shell deposited onto array of wurtzite ZnO nanowires. The shell is crystalline with orientation toward the ZnO growth axis, as demonstrated by X-ray linear dichroism. EXAFS analysis confirmed that more than 90% of Mn atoms substituted Zn in the shell while fraction of secondary phases was below 10%. The value of manganese spin magnetic moment was estimated from the Mn K{\beta} X-ray emission spectroscopy to be 4.3{\mu}B which is close to the theoretical value for substitutional Mn_Zn. However the analysis of L_2,3 x-ray magnetic circular dichroism data showed paramagnetic behaviour with saturated spin magnetic moment value of 1.95{\mu}B as determined directly from the spin sum rule. After quantitative analysis employing atomic multiplet simulations such difference was explained by a coexistence of paramagnetic phase and local antiferromagnetic coupling of Mn magnetic moments. Finally, spin-polarized electron density of states was probed by the spin-resolved Mn K-edge XANES spectroscopy and consequently analyzed by band structure calculations.Comment: Supplementary information available at http://www.rsc.org/suppdata/ja/c3/c3ja50153a/c3ja50153a.pdf J. Anal. At. Spectrom., 201

A Multi-scale Approach for Simulations of Kelvin Probe Force Microscopy with Atomic Resolution

The distance dependence and atomic-scale contrast observed in nominal contact potential difference (CPD) signals recorded by KPFM on surfaces of insulating and semiconducting samples, have stimulated theoretical attempts to explain such effects. We attack this problem in two steps. First, the electrostatics of the macroscopic tip-cantilever-sample system is treated by a finite-difference method on an adjustable nonuniform mesh. Then the resulting electric field under the tip apex is inserted into a series of atomistic wavelet-based density functional theory (DFT) calculations. Results are shown for a realistic neutral but reactive silicon nano-scale tip interacting with a NaCl(001) sample. Bias-dependent forces and resulting atomic displacements are computed to within an unprecedented accuracy. Theoretical expressions for amplitude modulation (AM) and frequency modulation (FM) KPFM signals and for the corresponding local contact potential differences (LCPD) are obtained by combining the macroscopic and atomistic contributions to the electrostatic force component generated at the voltage modulation frequency, and evaluated for several tip oscillation amplitudes A up to 10 nm. Being essentially constant over a few Volts, the slope of atomistic force versus bias is the basic quantity which determines variations of the atomic-scale LCPD contrast. Already above A = 0.1 nm, the LCPD contrasts in both modes exhibit almost the same spatial dependence as the slope. In the AM mode, this contrast is approximately proportional to $A^{-1/2}$, but remains much weaker than the contrast in the FM mode, which drops somewhat faster as A is increased. These trends are a consequence of the macroscopic contributions to the KPFM signal, which are stronger in the AM-mode and especially important if the sample is an insulator even at sub-nanometer separations where atomic-scale contrast appears.Comment: 19 pages, 13 figure