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 - Sahle, Christoph J. A1 - Niskanen, Johannes A1 - Schmidt, Christian A1 - Stefanski, Johannes A1 - Gilmore, Keith A1 - Forov, Yury A1 - Jahn, Sandro A1 - Wilke, Max A1 - Sternemann, Christian T1 - Cation Hydration in Supercritical NaOH and HCl Aqueous Solutions JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - 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. Y1 - 2017 U6 - https://doi.org/10.1021/acs.jpcb.7b09688 SN - 1520-6106 VL - 121 SP - 11383 EP - 11389 PB - American Chemical Society CY - Washington 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 -