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We present calculations on the quantum electrodynamics (QED) effects in 1s and 2s single and double ionization potentials of noble gases from Ne to Rn as perturbations on relativistic four-component Dirac-Fock wavefunctions. The most dominant effect originates from the self-energy of the core-electron that yields corrections of similar order as the transverse interaction. For 1s ionization potentials, a match within few eV against the known experimental values is obtained, and our work reveals considerable QED effects in the photoelectron binding energies across the periodic table-most strikingly even for Ne. We perform power-law fits for the corrections as a function of Z and interpolate the QED correction of similar to-0.55 eV for S1s. Due to this, the K-edge electron spectra of the third row and below need QED for a match in the absolute energy when using state-of-the-art instrumentation. Published by AIP Publishing.
Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water.
We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology. (C) 2017 Author(s).
The valence orbitals of aqueous histidine under basic, neutral and acidic conditions and their X-ray induced transformations have been monitored through N 1s resonant inelastic X-ray scattering. Using density functional ab initio molecular dynamics simulations in the core-hole state within the Z + 1 approximation, core-excitation-induced molecular transformations are quantified. Spectroscopic evidence for a highly directional X-ray-induced local N-H dissociation within the scattering duration is presented for acidic histidine. Our report demonstrates a protonation-state and chemical-environment dependent propensity for a molecular dissociation, which is induced by the absorption of high energy photons. This case study indicates that structural deformations in biomolecules under exposure to ionizing radiation, yielding possible alteration or loss of function, is highly dependent on the physiological state of the molecule upon irradiation.
We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe- Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures.