Deconvolving Instrumental and Intrinsic Broadening in Excited State X-ray Spectroscopies

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in excited-state spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy (XAS) measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering (XRS) and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy (RL) iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data. For the K-edge XAS of Ag, we find nearly complete removal of ~9.3 eV FWHM broadening from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm to these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.Comment: 35 pages, 13 figure

X-ray Raman scattering study of aligned polyfluorene

We present a non-resonant inelastic x-ray scattering study at the carbon K-edge on aligned poly[9,9-bis(2-ethylhexyl)-fluorene-2,7-diyl] and show that the x-ray Raman scattering technique can be used as a practical alternative to x-ray absorption measurements. We demonstrate that this novel method can be applied to studies on aligned $\pi$-conjugated polymers complementing diffraction and optical studies. Combining the experimental data and a very recently proposed theoretical scheme we demonstrate a unique property of x-ray Raman scattering by performing the symmetry decomposition on the density of unoccupied electronic states into $s$- and $p$-type symmetry contributions.Comment: 19 pages, 8 figure

Compton scattering beyond the impulse approximation

We treat the non-relativistic Compton scattering process in which an incoming photon scatters from an N-electron many-body state to yield an outgoing photon and a recoil electron, without invoking the commonly used frameworks of either the impulse approximation (IA) or the independent particle model (IPM). An expression for the associated triple differential scattering cross section is obtained in terms of Dyson orbitals, which give the overlap amplitudes between the N-electron initial state and the (N-1) electron singly ionized quantum states of the target. We show how in the high energy transfer regime, one can recover from our general formalism the standard IA based formula for the cross section which involves the ground state electron momentum density (EMD) of the initial state. Our formalism will permit the analysis and interpretation of electronic transitions in correlated electron systems via inelastic x-ray scattering (IXS) spectroscopy beyond the constraints of the IA and the IPM.Comment: 7 pages, 1 figur

Hydration in aqueous osmolyte solutions: the case of TMAO and urea

The hydration and hydrogen-bond topology of small water solvated molecules such as the naturally occurring organic osmolytes trimethylamine N-oxide (TMAO) and urea are under intense investigation. We aim at furthering the understanding of this complex hydration by combining experimental oxygen K-edge excitation spectra with results from spectra calculated via the Bethe-Salpeter equation based on structures obtained from ab initio molecular dynamics simulations. Comparison of experimental and calculated spectra allows us to extract detailed information about the immediate surrounding of the solute molecules in the solvated state. We quantify and localize the influence of the solute on the hydrogen bond network of the water solvent and find spectroscopic fingerprints of a clear directional asymmetry around TMAO with strong and local kosmotropic influence around TMAO's NO head group and slight chaotropic influence around the hydrophobic methyl groups. The influence of urea on the local water network is qualitatively similar to that of TMAO but weaker in magnitude. The strongest influence of both molecules on the shape of the oxygen K-edge spectra is found in the first hydration shells

X-ray Raman scattering : An exciting tool for the study of matter at conditions of the Earth's interior

Volume: 425The study of minerals and melts at in situ conditions is highly relevant to understand the physical and chemical properties of the Earth's crust and mantle. Here, x-ray Raman scattering provides a valuable tool to investigate the local atomic and electronic structure of Earth materials consisting predominantly of low Z elements at high pressures and temperatures. The capabilities of x-ray Raman scattering to investigate silicate minerals, glasses, and melts are discussed and the application of the method to in situ studies of silicate melts using a hydrothermal diamond anvil cell is demonstrated.Non peer reviewe

Pregnancy-induced maternal microchimerism shapes neurodevelopment and behavior in mice

Life-long brain function and mental health are critically determined by developmental processes occurring before birth. During mammalian pregnancy, maternal cells are transferred to the fetus. They are referred to as maternal microchimeric cells (MMc). Among other organs, MMc seed into the fetal brain, where their function is unknown. Here, we show that, in the offspring's developing brain in mice, MMc express a unique signature of sensome markers, control microglia homeostasis and prevent excessive presynaptic elimination. Further, MMc facilitate the oscillatory entrainment of developing prefrontal-hippocampal circuits and support the maturation of behavioral abilities. Our findings highlight that MMc are not a mere placental leak out, but rather a functional mechanism that shapes optimal conditions for healthy brain function later in life

Electron-density dependence of double-plasmon excitations in simple metals

Double plasmons are unique fingerprints of dynamical correlations in the model of a free-electron gas beyond the random phase approximation. A combined experimental and theoretical study of double-plasmon excitations in three simple metals Na, Mg, and Al is presented. The intensities, spectral shapes, and dispersions of these excitations are analyzed as a function of momentum. The measured double-plasmon intensity is found to increase with a decreasing electron density, which is in good agreement with the expectations of strength of the correlation effects as a function of the electron gas density. The overall quantitative agreement between the experimental and the theoretical results is very good, while the remaining discrepancies may be due to higher order correlation effects and band-structure effects

Correlation-Induced Double-Plasmon Excitation in Simple Metals Studied by Inelastic X-Ray Scattering

We report a new type of peaklike structure observed in the tail of the dynamic structure factor of simple metals, measured by inelastic x-ray scattering. Based on the momentum-transfer dependence of the energy position and the intensity of this structure, it has been unambiguously attributed to intrinsic plasmon-plasmon excitations, an electronic correlation effect that was theoretically predicted by many-body perturbation theory of the homogeneous-electron-gas model beyond the random-phase approximation. This signature appears to be largely unaffected by electron-ion interaction effects. Thus a structure that is primarily caused by correlation effects in the electron gas has been found experimentally in the dynamic structure factor of simple metals