TY - JOUR A1 - Sternemann, C. A1 - Wilke, Max T1 - Spectroscopy of low and intermediate Z elements at extreme conditions: in situ studies of Earth materials at pressure and temperature via X-ray Raman scattering JF - High pressure research N2 - X-ray Raman scattering spectroscopy is an emerging method in the study of low and intermediate Z elements' core-electron excitations at extreme conditions in order to reveal information on local structure and electronic state of matter in situ. We discuss the capabilities of this method to address questions in Earth materials' science and demonstrate its sensitivity to detect changes in the oxidation state, electronic structure, coordination, and spin state. Examples are presented for the study of the oxygen K-, silicon L- and iron M-edges. We assess the application of both temperature and pressure in such investigations exploiting diamond anvil cells in combination with resistive or laser heating which is required to achieve realistic conditions of the Earth's crust, mantle, and core. KW - X-ray Raman scattering KW - inelastic X-ray scattering KW - X-ray absorption KW - high pressure research KW - diamond anvil cell KW - minerals KW - glasses KW - melts KW - Earth materials KW - spin transition KW - bonding transition KW - coordination transformation KW - oxidation state KW - electronic structure Y1 - 2016 U6 - https://doi.org/10.1080/08957959.2016.1198903 SN - 0895-7959 SN - 1477-2299 VL - 36 SP - 275 EP - 292 PB - IOP Publ. Ltd. CY - Abingdon ER - TY - JOUR A1 - Spiekermann, Georg A1 - Wilke, Max A1 - Jahn, Sandro T1 - Structural and dynamical properties of supercritical H2O-SiO2 fluids studied by ab initio molecular dynamics JF - Chemical geology : official journal of the European Association for Geochemistry N2 - In this study we report the structure of supercritical H2O-SiO2 fluid composed of 50 mol% H2O and 50 mol% SiO2 at 3000 K and 2400 K. investigated by means of ab initio molecular dynamics of models comprising 192 and 96 atoms. The density is set constant to 138 g/cm(3), which yields a pressure of 4.3 GPa at 3000 K and 3.6 GPa at 2400 K. Throughout the trajec[ories, water molecules are formed and dissociated via the network modifying reaction 2 SiOH = SiOSi + H2O The calculation of the reaction constant K- [OH](2)/[H2O][O2-] is carried out on the basis of the experimentally relevant Q ' species notation and agrees well with an extrapolation of experimental data to 3000 K. After quench from 3000 K to 2400 K, the degree of polymerization of the silicate network in the 192-atom models increases noticeably within several tens of picoseconds, accompanied by release of molecular H2O. An unexpected opposite trend is observed in smaller 96-atom models, due to a finite size effect, as several uncorrelated models of 192 and 96 atoms indicate. The temperature-dependent slowing down of the H2O-silica interaction dynamics is described on the basis of the bond autocorrelation function. (C) 2016 Elsevier B.V. All rights reserved. KW - Fluid KW - SiO2-H2O KW - SiO(2)Molecular dynamics KW - Polymerization KW - DFT Y1 - 2016 U6 - https://doi.org/10.1016/j.chemgeo.2016.01.010 SN - 0009-2541 SN - 1878-5999 VL - 426 SP - 85 EP - 94 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Schaffer, Mario A1 - Idzik, Krzysztof R. A1 - Wilke, Max A1 - Licha, Tobias T1 - Amides as thermo-sensitive tracers for investigating the thermal state of geothermal reservoirs JF - Geothermics : an international journal of geothermal research and its applications N2 - The application of thermo-sensitive tracers is a promising technique for evaluating the thermal state of geothermal reservoirs. To extend the compound spectrum for hydrolyzable compounds to reservoir temperatures between 100 and 200 degrees C carboxamides were studied. The kinetic parameters of 17 self-synthesized amides were determined in hydrothermal batch and autoclave experiments. The influence of the molecular structure and the role of pH/pOH on hydrolysis kinetics were studied. Additionally, the thermal stabilities of the hydrolysis products were evaluated. The results demonstrate the high potential of tracers based on amide hydrolysis for use in medium enthalpy reservoirs. (C) 2016 Elsevier Ltd. All rights reserved. KW - Thermo-sensitive tracers KW - Amides KW - Hydrolysis KW - Kinetics KW - Reservoir temperature KW - Molecular design Y1 - 2016 U6 - https://doi.org/10.1016/j.geothermics.2016.05.004 SN - 0375-6505 SN - 1879-3576 VL - 64 SP - 180 EP - 186 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Rosa, A. D. A1 - Pohlenz, Julia A1 - de Grouchy, C. A1 - Cochain, B. A1 - Kono, Y. A1 - Pasternak, S. A1 - Mathon, O. A1 - Irifune, T. A1 - Wilke, Max T1 - In situ characterization of liquid network structures at high pressure and temperature using X-ray absorption spectroscopy coupled with the Paris-Edinburgh press JF - High pressure research N2 - We review recent progress in studying structural properties of liquids using X-ray absorption spectroscopy coupled with the Paris-Edinburgh press at third-generation synchrotron facilities. This experimental method allows for detecting subtle changes in atomic arrangements of melts over a wide pressure-temperature range. It has been also employed to monitor variations of the local coordination environment of diluted species contained in glasses, liquids and crystalline phases as a function of the pressure and temperature. Such information is of great importance for gaining deeper insights into the physico-chemical properties of liquids at extreme condition, including the understanding of such phenomena as liquid-liquid phase transitions, viscosity drops and various transport properties of geological melts. Here, we describe the experimental approach and discuss its potential in structural characterization on selected scientific highlights. Finally, the current ongoing instrumental developments and future scientific opportunities are discussed. KW - X-ray absorption KW - Paris-Edinburgh press KW - liquid structure KW - high pressure and temperature KW - EXAFS Y1 - 2016 U6 - https://doi.org/10.1080/08957959.2016.1199693 SN - 0895-7959 SN - 1477-2299 VL - 36 SP - 332 EP - 347 PB - American Geophysical Union CY - Abingdon ER - TY - GEN A1 - Qiu, Chen A1 - Krüger, Yves A1 - Wilke, Max A1 - Marti, Dominik A1 - Rička, Jaro A1 - Frenz, Martin T1 - Exploration of the phase diagram of liquid water in the low-temperature metastable region using synthetic fluid inclusions N2 - We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996–916 kg m−3) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid–vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid–vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m−3 remains in a homogeneous state during cooling down to a temperature of −30.5 °C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 °C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the ϱ–T plane at around 40 °C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p–V–T properties of metastable water in the low-temperature region. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 327 Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-394993 ER - TY - JOUR A1 - Qiu, C. A1 - Krüger, Y. A1 - Wilke, Max A1 - Marti, D. A1 - Ricka, J. A1 - Frenz, M. T1 - Exploration of the phase diagram of liquid water in the low-temperature metastable region using synthetic fluid inclusions JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996-916 kg m(-3)) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid-vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid-vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m(-3) remains in a homogeneous state during cooling down to a temperature of -30.5 degrees C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 degrees C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the R-T plane at around 40 degrees C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p-V-T properties of metastable water in the low-temperature region. Y1 - 2016 U6 - https://doi.org/10.1039/c6cp04250c SN - 1463-9076 SN - 1463-9084 VL - 18 SP - 28227 EP - 28241 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Grüneberger, Anja Maria A1 - Schmidt, Christian A1 - Jahn, Sandro A1 - Rhede, Dieter A1 - Loges, Anselm A1 - Wilke, Max T1 - Interpretation of Raman spectra of the zircon-hafnon solid solution JF - European journal of mineralogy N2 - Zircon (ZrSiO4), hafnon (HfSiO4) and five intermediate compositions were synthesized from a Pb silicate melt. The resulting crystals were 20-300 mu m in size and displayed sector and growth zoning. Raman spectra were acquired at locations in the sample for which preceding electron microprobe (EMP) analyses revealed sufficient compositional homogeneity. The dataset documents shifts of Raman bands with changing composition. In this study, bands that have previously not been reported were found for the intermediate compositions and for pure hafnon, in particular at wavenumbers less than 200 cm(-1). For these external modes, the dataset provides new insight into the compositional dependence of their frequencies. Density-functional theory calculations support the observations and are used for a detailed interpretation of the spectra. The pitfalls of the EMP analysis along the zircon-hafnon join are highlighted. KW - zircon KW - hafnon KW - solid solution KW - Raman spectroscopy KW - synthesis KW - density-functional theory KW - hafnium analysis Y1 - 2016 U6 - https://doi.org/10.1127/ejm/2016/0028-2551 SN - 0935-1221 SN - 1617-4011 VL - 28 SP - 721 EP - 733 PB - Schweizerbart CY - Stuttgart ER -