@article{TaranNunezValdezEfthimiopoulosetal.2019,
  author    = {Taran, Michail N. and Nunez Valdez, Maribel and Efthimiopoulos, Ilias and M{\"u}ller, J. and Reichmann, Hans-Josef and Wilke, Max and Koch-M{\"u}ller, Monika},
  title     = {Spectroscopic and ab initio studies of the pressure-induced Fe2+ high-spin-to-low-spin electronic transition in natural triphylite-lithiophilite},
  series = {Physics and Chemistry of Minerals},
  volume    = {46},
  journal   = {Physics and Chemistry of Minerals},
  number    = {3},
  publisher = {Springer},
  address   = {New York},
  issn      = {0342-1791},
  doi       = {10.1007/s00269-018-1001-y},
  pages     = {245 -- 258},
  year      = {2019},
  abstract  = {Using optical absorption and Raman spectroscopic measurements, in conjunction with the first-principles calculations, a pressure-induced high-spin (HS)-to-low-spin (LS) state electronic transition of Fe2+ (M2-octahedral site) was resolved around 76-80GPa in a natural triphylite-lithiophilite sample with chemical composition (LiFe0.7082+Mn0.292PO4)-Li-M1-Fe-M2 (theoretical composition (LiFe0.52+Mn0.5PO4)-Li-M1-Fe-M2). The optical absorption spectra at ambient conditions consist of a broad doublet band with two constituents (1) (similar to 9330cm(-1)) and (2) (similar to 7110cm(-1)), resulting from the electronic spin-allowed transition (T2gEg)-T-5-E-5 of octahedral (HSFe2+)-Fe-M2. Both (1) and (2) bands shift non-linearly with pressure to higher energies up to similar to 55GPa. In the optical absorption spectrum measured at similar to 81GPa, the aforementioned HS-related bands disappear, whereas a new broadband with an intensity maximum close to 16,360cm(-1) appears, superimposed on the tail of the high-energy ligand-to-metal O2-Fe2+ charge-transfer absorption edge. We assign this new band to the electronic spin-allowed dd-transition (1)A(1g)(1)T(1g) of LS Fe2+ in octahedral coordination. The high-pressure Raman spectra evidence the Fe2+ HS-to-LS transition mainly from the abrupt shift of the P-O symmetric stretching modes to lower frequencies at similar to 76GPa, the highest pressure achieved in the Raman spectroscopic experiments. Calculations indicated that the presence of Mn-M2(2+) simply shifts the isostructural HS-to-LS transition to higher pressures compared to the triphylite Fe-M2(2+) end-member, in qualitative agreement with our experimental observations.},
  language  = {en}
}
@article{SpiekermannWilkeJahn2016,
  author    = {Spiekermann, Georg and Wilke, Max and Jahn, Sandro},
  title     = {Structural and dynamical properties of supercritical H2O-SiO2 fluids studied by ab initio molecular dynamics},
  series = {Chemical geology : official journal of the European Association for Geochemistry},
  volume    = {426},
  journal   = {Chemical geology : official journal of the European Association for Geochemistry},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0009-2541},
  doi       = {10.1016/j.chemgeo.2016.01.010},
  pages     = {85 -- 94},
  year      = {2016},
  abstract  = {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.},
  language  = {en}
}