skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

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 Å3. The measurements were conducted at a spatial resolution corresponding to Qmax = 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 density of 0.0333 molecules per Å3 and Qmax = 20 Å-1 [J Chem Phys 138, 074506 (2013)]1 and at 70°C having density of 0.0327 molecules per Å3 and Qmax = 20 Å-1. [J Chem Phys 141, 214507 (2014)]2 The structure of water is very different at these three different T and P state points and thus they provide basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3-3 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 bymore » both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005 and mW). The DFT-based, revPBE-D3 provides the best overall representation of the ambient, high-temperature and high-pressure data while the TIP4P/2005 also captures the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which 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. Acknowledgments: Thanks to Rick Spence and Doug Robinson for support with the beamline equipment at the Advanced Photon Source. The helpful comments of Valeria Molinero are acknowledged. This work was supported by the U.S. Department of Energy (DOE) office of Basic Energy Sciences grant Number BES DE-FG02-09ER46650 which supported, MD simulations, data analysis and manuscript preparation (LBS and JBP). DOE contract DE-AC02-06CH11357 supports operation of the Advanced Photon Source at Argonne National Laboratory. Work by JLF, MG, GSK and CJM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Authors:
ORCiD logo; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1337266
Report Number(s):
PNNL-SA-115506
Journal ID: ISSN 0021-9606; KC0301050
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Skinner, L. B., Galib, M., Fulton, J. L., Mundy, C. J., Parise, J. B., Pham, V. -T., Schenter, G. K., and Benmore, C. J. The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation. United States: N. p., 2016. Web. doi: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. The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation. United States. https://doi.org/10.1063/1.4944935
Skinner, L. B., Galib, M., Fulton, J. L., Mundy, C. J., Parise, J. B., Pham, V. -T., Schenter, G. K., and 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". United States. https://doi.org/10.1063/1.4944935.
@article{osti_1337266,
title = {The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation},
author = {Skinner, L. B. and Galib, M. and Fulton, J. L. and Mundy, C. J. and Parise, J. B. and Pham, V. -T. and Schenter, G. K. and Benmore, C. J.},
abstractNote = {X-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å3. The measurements were conducted at a spatial resolution corresponding to Qmax = 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 density of 0.0333 molecules per Å3 and Qmax = 20 Å-1 [J Chem Phys 138, 074506 (2013)]1 and at 70°C having density of 0.0327 molecules per Å3 and Qmax = 20 Å-1. [J Chem Phys 141, 214507 (2014)]2 The structure of water is very different at these three different T and P state points and thus they provide basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3-3 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 and mW). The DFT-based, revPBE-D3 provides the best overall representation of the ambient, high-temperature and high-pressure data while the TIP4P/2005 also captures the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which 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. Acknowledgments: Thanks to Rick Spence and Doug Robinson for support with the beamline equipment at the Advanced Photon Source. The helpful comments of Valeria Molinero are acknowledged. This work was supported by the U.S. Department of Energy (DOE) office of Basic Energy Sciences grant Number BES DE-FG02-09ER46650 which supported, MD simulations, data analysis and manuscript preparation (LBS and JBP). DOE contract DE-AC02-06CH11357 supports operation of the Advanced Photon Source at Argonne National Laboratory. Work by JLF, MG, GSK and CJM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.},
doi = {10.1063/1.4944935},
url = {https://www.osti.gov/biblio/1337266}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 144,
place = {United States},
year = {Thu Apr 07 00:00:00 EDT 2016},
month = {Thu Apr 07 00:00:00 EDT 2016}
}

Works referenced in this record:

Communications: High-temperature water under pressure
journal, March 2010


Changes of structure and dipole moment of water with temperature and pressure: A first principles study
journal, July 2011


Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q -range
journal, February 2013


Persistent Ion Pairing in Aqueous Hydrochloric Acid
journal, June 2014


Is Iodate a Strongly Hydrated Cation?
journal, October 2011


Short-range structural transformations in water at high pressures
journal, April 2011


Structure of liquid water at high pressures and temperatures
journal, October 2002


X‐ray scattering in liquid water at pressures of up to 7.7 kbar: Test of a fluctuation model
journal, January 1994


Intermediate range chemical ordering in amorphous and liquid water, Si, and Ge
journal, October 2005


Adding a Length Scale to the Polyamorphic Ice Debate
journal, September 2006


The structure of water around the compressibility minimum
journal, December 2014


X-ray diffraction studies on the structure of water at high temperatures and pressures
journal, January 1996


Structure of liquid water under high pressure up to 17 GPa
journal, January 2010


Structures of High-Density and Low-Density Water
journal, March 2000


Packing and the structural transformations in liquid and amorphous oxides from ambient to extreme conditions
journal, June 2014


Area detector corrections for high quality synchrotron X-ray structure factor measurements
journal, January 2012

  • Skinner, Lawrie B.; Benmore, Chris J.; Parise, John B.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 662, Issue 1
  • https://doi.org/10.1016/j.nima.2011.09.031

Chemical binding and electron correlation effects in x‐ray and high energy electron scattering
journal, September 1994


What can x-ray scattering tell us about the radial distribution functions of water?
journal, November 2000


Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005


Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010


Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007


A general purpose model for the condensed phases of water: TIP4P/2005
journal, December 2005


DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism
journal, January 2006


Water Modeled As an Intermediate Element between Carbon and Silicon
journal, April 2009


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Development of a “First-Principles” Water Potential with Flexible Monomers. III. Liquid Phase Properties
journal, July 2014


On the representation of many-body interactions in water
journal, September 2015


On the Simulation of Quantum Systems: Path Integral Methods
journal, October 1986


The comparison of molecular dynamics simulations with diffraction experiments
journal, January 1993


A quantitative account of quantum effects in liquid water
journal, October 2006


Novel stable crystalline phase for the Stillinger-Weber potential
journal, July 2014


Coarse-Graining of TIP4P/2005, TIP4P-Ew, SPC/E, and TIP3P to Monatomic Anisotropic Water Models Using Relative Entropy Minimization
journal, August 2014


Structures of High and Low Density Amorphous Ice by Neutron Diffraction
journal, May 2002


Relationship between structural order and the anomalies of liquid water
journal, January 2001


Works referencing / citing this record:

Coherent X-rays reveal the influence of cage effects on ultrafast water dynamics
journal, May 2018


Revisiting the hydration structure of aqueous Na +
journal, February 2017


Mass density fluctuations in quantum and classical descriptions of liquid water
journal, June 2017


Toward chemical accuracy in the description of ion–water interactions through many-body representations. Alkali-water dimer potential energy surfaces
journal, October 2017


Unraveling the spectral signatures of solvent ordering in K-edge XANES of aqueous Na +
journal, September 2018


Mass density fluctuations in quantum and classical descriptions of liquid water
text, January 2017


Coherent X-rays reveal the influence of cage effects on ultrafast water dynamics
text, January 2018


Mass Density Fluctuations in Quantum and Classical descriptions of Liquid Water
text, January 2017


Coherent X-rays reveal the influence of cage effects on ultrafast water dynamics
text, January 2018