Alexander Nyrow

Microscopic structure of water at elevated pressures and temperatures

We report on the microscopic structure of water at sub- and supercritical conditions studied using X-ray Raman spectroscopy, ab initio molecular dynamics simulations, and density functional theory. Systematic changes in the X-ray Raman spectra with increasing pressure and temperature are observed. Throughout the studied thermodynamic range, the experimental spectra can be interpreted with a structural model obtained from the molecular dynamics simulations. A spatial statistical analysis using Ripley’s K-function shows that this model is homogeneous on the nanometer length scale. According to the simulations, distortions of the hydrogen-bond network increase dramatically when temperature and pressure increase to the supercritical regime. In particular, the average number of hydrogen bonds per molecule decreases to ≈0.6 at 600 °C and p = 134 MPa.

Pressure induced spin transition revealed by iron M2,3-edge spectroscopy

We present a method to characterize pressure induced magnetic high to low spin transition in iron sulphide using x-ray Raman scattering spectroscopy at the iron M2,3-edge. The advantage of this method is that the observed spectral changes between pressures of 1.7 GPa and 10.1 GPa can be used with the help of atomic multiplet calculations to determine the crystal field splitting parameters associated with the spin transition. We discuss the potential of this M2,3-edge spectroscopy to investigate the irons electronic spin state in-situ at the conditions of the inner Earth, i.e., at high temperature and high pressure, providing exciting opportunities for geophysical and materials science applications.

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

The study of minerals and melts at in situ conditions is highly relevant to understand the physical and chemical properties of the Earths 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.

Bulk sensitive determination of the Fe3+/FeTot-ratio in minerals by Fe L2/3-edge X-ray Raman scattering

We present the first measurements of the iron L2/3-edge of the compounds FeO, Fe2O3, and Fe3O4 at ambient pressure and of FeCO3 at high pressures of 2.4 and 40 GPa using a diamond anvil cell by X-ray Raman scattering spectroscopy, a bulk sensitive probe of soft X-ray absorption edges making use of hard X-rays. We show that the spectral shape of the Fe L2/3-edge can be analyzed quantitatively to reveal the oxidation state of iron in matter. Consequently, in situ X-ray Raman scattering spectroscopy at the iron L-edge at high pressure and temperature opens exciting perspectives to characterize the local coordination, oxidation, and spin state of iron at high pressure and temperature, conditions that are of relevance for e.g. geological sciences or chemical processing.

Structural changes in amorphous Ge x SiO y on the way to nanocrystal formation

Temperature induced changes of the local chemical structure of bulk amorphous GexSiOy are studied by Ge K-edge x-ray absorption near-edge spectroscopy and Si L2/3-edge x-ray Raman scattering spectroscopy. Different processes are revealed which lead to formation of Ge regions embedded in a Si oxide matrix due to different initial structures of as-prepared samples, depending on their Ge/Si/O ratio and temperature treatment, eventually resulting in the occurrence of nanocrystals. Here, disproportionation of GeOx and SiOx regions and/or reduction of Ge oxides by pure Si or by a surrounding Si sub-oxide matrix can be employed to tune the size of Ge nanocrystals along with the chemical composition of the embedding matrix. This is important for the optimization of the electronic and luminescent properties of the material.

Influence of hydrogen on thermally induced phase separation in GeO/SiO2 multilayers.

The influence of the annealing atmosphere on the temperature induced phase separation of Ge oxide in GeO(x)/SiO(2) multilayers (x≈1), leading to size controlled growth of Ge nanocrystals, is explored by means of x-ray absorption spectroscopy at the Ge K-edge. Ge sub-oxides contained in the as-deposited multilayers diminish with increasing annealing temperature, showing complete phase separation at approximately 450 °C using inert N(2) ambient. The use of reducing H(2) in the annealing atmosphere influences the phase separation even at an early stage of the disproportionation. In particular, the temperature regime where the phase separation occurs is lowered by at least 50 °C. At temperatures above 400 °C the sublayer composition, and thus the density of the Ge nanocrystals, can be altered by making use of the reduction of GeO(2) by H(2).