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Title: Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [3]
  1. Univ. of Chicago, IL (United States)
  2. Hong Kong Univ. of Science and Technology (China)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
+ Show Author Affiliations

The phase diagram of water at extreme conditions plays a critical role in Earth and planetary science, yet remains poorly understood. Here we report a first-principles investigation of the liquid at high temperature, between 11 GPa and 20 GPa—a region where numerous controversial results have been reported over the past three decades. Our results are consistent with the recent estimates of the water melting line below 1,000 K and show that on the 1,000-K isotherm the liquid is rapidly dissociating and recombining through a bimolecular mechanism. We found that short-lived ionic species act as charge carriers, giving rise to an ionic conductivity that at 11 GPa and 20 GPa is six and seven orders of magnitude larger, respectively, than at ambient conditions. Conductivity calculations were performed entirely from first principles, with no a priori assumptions on the nature of charge carriers. Despite frequent dissociative events, we observed that hydrogen bonding persists at high pressure, up to at least 20 GPa. Our computed Raman spectra, which are in excellent agreement with experiment, show no distinctive signatures of the hydronium and hydroxide ions present in our simulations. Instead, we found that infrared spectra are sensitive probes of molecular dissociation, exhibiting a broad band below the OH stretching mode ascribable to vibrations of complex ions.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC); Alfred P. Sloan Foundation; Midwest Integrated Center for Computational Materials (MICCoM)
Grant/Contract Number:
AC02-06CH11357; BES 5J-30161-0010A
OSTI ID:
1454668
Alternate ID(s):
OSTI ID: 1489500
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 115, Issue 27; ISSN 0027-8424
Publisher:
National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 34 works
Citation information provided by
Web of Science

References (59)

Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics journal July 2014
Melting of ice under pressure journal September 2008
High P – T Brillouin scattering study of H 2 O melting to 26 GPa journal May 2014
Generalized Gradient Approximation Made Simple journal October 1996
The Structure of Electronic Excitation Levels in Insulating Crystals journal August 1937
Extended and accurate determination of the melting curves of argon, helium, ice ( H 2 O ) , and hydrogen ( H 2 ) journal March 2000
Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth’s deep mantle journal March 2018
Estimating the quantum effects from molecular vibrations of water under high pressures and temperatures journal August 2009
Calculated frequencies and intensities associated with coupling of the proton motion with the hydrogen bond stretching vibration in a double minimum potential surface journal January 1973
High pressure-temperature Raman measurements of H[sub 2]O melting to 22 GPa and 900 K journal January 2004
IR spectral assignments for the hydrated excess proton in liquid water journal April 2017
Raman Spectra of Liquid Water from Ab Initio Molecular Dynamics: Vibrational Signatures of Charge Fluctuations in the Hydrogen Bond Network journal August 2013
Catalytic behaviour of dense hot water journal March 2009
Hydrogen-bond kinetics in liquid water journal January 1996
Whole-cell heater for the diamond anvil cell journal July 2003
Ab initio simulation of the equation of state and kinetics of shocked water journal March 2009
Ultrafast 2D IR spectroscopy of the excess proton in liquid water journal October 2015
H2O: another ice phase and its melting curve journal September 2008
Optimally smooth norm-conserving pseudopotentials journal December 1985
i-PI: A Python interface for ab initio path integral molecular dynamics simulations journal March 2014
Stability of hydrous silicate at high pressures and water transport to the deep lower mantle journal February 2014
The refractive index and electronic gap of water and ice increase with increasing pressure journal May 2014
Decomposition of the Experimental Raman and Infrared Spectra of Acidic Water into Proton, Special Pair, and Counterion Contributions journal October 2017
Electrical Conductivity of Mantle Minerals: Role of Water in Conductivity Anomalies journal May 2013
Possible presence of high-pressure ice in cold subducting slabs journal December 2000
Plastic crystal phases of simple water models journal June 2009
Dissociative melting of ice VII at high pressure journal March 2009
Phase Diagram and Electrical Conductivity of High Energy-Density Water from Density Functional Theory journal July 2006
Phase diagram of H2O: Thermodynamic functions of the phase transitions of high-pressure ices journal June 2010
Translational and Rotational Diffusion in Water in the Gigapascal Range journal October 2013
The Fundamental Conductivity and Resistivity of Water journal January 2005
The Hydrated Excess Proton in the Zundel Cation H 5 O 2 + : The Role of Ultrafast Solvent Fluctuations journal July 2016
Comment on “Dissociation of Water under Pressure” journal October 2002
Canonical sampling through velocity rescaling journal January 2007
Communications: High-temperature water under pressure journal March 2010
Phonons and related crystal properties from density-functional perturbation theory journal July 2001
Computation of Maximally Localized Wannier Functions using a simultaneous diagonalization algorithm journal September 2003
Spontaneous Raman Scattering from Shocked Water journal November 1985
A plastic phase of water from computer simulation journal May 2008
Superionic and Metallic States of Water and Ammonia at Giant Planet Conditions journal January 1999
First-Principles Calculation of Transport Coefficients journal December 1998
Dynamic Ionization of Water under Extreme Conditions journal April 2005
Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth journal March 2013
Reevaluating carbon fluxes in subduction zones, what goes down, mostly comes up journal June 2015
Melting curve of H 2 O to 90 GPa measured in a laser-heated diamond cell journal March 2004
Melting behavior of H 2 O at high pressures and temperatures journal January 2005
Constraining the equation of state of fluid H2O to 80 GPa using the melting curve, bulk modulus, and thermal expansivity of Ice VII journal July 2004
Equation of state and electrical conductivity of water and ammonia shocked to the 100 GPa (1 Mbar) pressure range journal June 1982
Dissociation of Water under Pressure journal December 2001
Dynamical Screening and Ionic Conductivity in Water from Ab Initio Simulations journal October 2011
Electrical conductivity of water in shock compression journal January 1966
The fate of carbon dioxide in water-rich fluids under extreme conditions journal October 2016
Diffusion and electrical conductivity in water at ultrahigh pressures journal November 2010
The Hydrated Excess Proton in the Zundel Cation H 5 O 2 + : The Role of Ultrafast Solvent Fluctuations journal July 2016
Dissociation of Water under Pressure text January 2001
Comment on “Dissociation of Water under Pressure” text January 2002
i-PI: A Python interface for ab initio path integral molecular dynamics simulations text January 2014
The refractive index and electronic gap of water and ice increase with increasing pressure text January 2014
The first principles calculation of transport coefficients text January 1998

Cited By (5)

Understanding the phase separation of N 2 /H 2 O and CO 2 /H 2 O binary systems through reactive force fields-based molecular dynamics simulations journal December 2018
Mid-IR spectroscopy of supercritical water: From dilute gas to dense fluid journal February 2019
Ambient conditions disordered-ordered phase transition of two-dimensional interfacial water molecules dependent on charge dipole moment journal June 2019
Temperature effects on the ionic conductivity in concentrated alkaline electrolyte solutions text January 2019
Yttrium speciation in subduction-zone fluids from ab initio molecular dynamics simulations journal May 2020

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36 MATERIALS SCIENCE
ab initio spectroscopy
first-principles simulation
high-pressure water
ionic conductivity