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Skinner LB, Galib M, Fulton JL, et al. The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation. J Chem Phys. 2016;144(13):134504doi: 10.1063/1.4944935.
Skinner, L. B., Galib, M., Fulton, J. L., Mundy, C. J., Parise, J. B., Pham, V. T., Schenter, G. K., & Benmore, C. J. (2016). The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation. The Journal of chemical physics, 144(13), 134504. https://doi.org/10.1063/1.4944935
Skinner, L B, et al. "The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation." The Journal of chemical physics vol. 144,13 (2016): 134504. doi: https://doi.org/10.1063/1.4944935
Skinner LB, Galib M, Fulton JL, Mundy CJ, Parise JB, Pham VT, Schenter GK, Benmore CJ. The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation. J Chem Phys. 2016 Apr 07;144(13):134504. doi: 10.1063/1.4944935. PMID: 27059577.
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J Chem Phys. 2016 Apr 07;144(13):134504. doi: 10.1063/1.4944935.

The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation.

The Journal of chemical physics

L B Skinner, M Galib, J L Fulton, C J Mundy, J B Parise, V-T Pham, G K Schenter, C J Benmore

Affiliations

  1. X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.
  2. Physical and Computational Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, USA.
  3. Mineral Physics Institute, Stony Brook University, Stony Brook, New York, New York 11794-2100, USA.
  4. Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP48, 91192 Gif-sur-Yvette, France.

PMID: 27059577 DOI: 10.1063/1.4944935

Abstract

X-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å(3). The measurements were conducted at a spatial resolution corresponding to Q(max) = 16 Å(-1). The method of data analysis and measurement in this study follows the earlier benchmark results reported for water under ambient conditions having a density of 0.0333 molecules per Å(3) and Q(max) = 20 Å(-1) [J. Chem. Phys. 138, 074506 (2013)] and at 70 °C having a density of 0.0327 molecules per Å(3) and Q(max) = 20 Å(-1) [J. Chem. Phys. 141, 214507 (2014)]. The structure of water is very different at these three different T and P state points and thus they provide the basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3 and 3 Å are nearly unchanged: the peak position, shape, and coordination number are nearly identical to their values under ambient conditions. However, in the region above 3 Å, large structural changes occur with the collapse of the well-defined 2nd shell and shifting of higher shells to shorter distances. The measured structure is compared to simulated structure using intermolecular potentials described by both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005, MB-pol, and mW). The DFT-based, revPBE-D3, method and the many-body empirical potential model, MB-pol, provide the best overall representation of the ambient, high-temperature, and high-pressure data. The revPBE-D3, MB-pol, and the TIP4P/2005 models capture the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which partially encroaches the 1st shell at ambient pressure, is pushed further into the local tetrahedral arrangement at higher pressures by the more distant molecules filling the void space in the network between the 1st and 2nd shells.

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