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

Abstract

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 broadmore » band below the OH stretching mode ascribable to vibrations of complex ions.« less

Authors:
ORCiD logo; ORCiD logo; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
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)
OSTI Identifier:
1454668
Alternate Identifier(s):
OSTI ID: 1489500
Grant/Contract Number:  
BES 5J-30161-0010A; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 27; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ab initio spectroscopy; first-principles simulation; high-pressure water; ionic conductivity

Citation Formats

Rozsa, Viktor, Pan, Ding, Giberti, Federico, and Galli, Giulia. Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions. United States: N. p., 2018. Web. doi:10.1073/pnas.1800123115.
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Rozsa, Viktor, Pan, Ding, Giberti, Federico, & Galli, Giulia. Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions. United States. https://doi.org/10.1073/pnas.1800123115
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Rozsa, Viktor, Pan, Ding, Giberti, Federico, and Galli, Giulia. Mon . "Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions". United States. https://doi.org/10.1073/pnas.1800123115.
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@article{osti_1454668,
title = {Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions},
author = {Rozsa, Viktor and Pan, Ding and Giberti, Federico and Galli, Giulia},
abstractNote = {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.},
doi = {10.1073/pnas.1800123115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 27,
volume = 115,
place = {United States},
year = {Mon Jun 18 00:00:00 EDT 2018},
month = {Mon Jun 18 00:00:00 EDT 2018}
}
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https://doi.org/10.1073/pnas.1800123115
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