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Title: Liquid water is a dynamic polydisperse branched polymer

Abstract

We developed the RexPoN force field for water based entirely on quantum mechanics. It predicts the properties of water extremely accurately, withTmelt= 273.3 K (273.15 K) and properties at 298 K: ΔHvap= 10.36 kcal/mol (10.52), density = 0.9965 g/cm3 (0.9965), entropy = 68.4 J/mol/K (69.9), and dielectric constant = 76.1 (78.4), where experimental values are in parentheses. Upon heating from 0.0 K (ice) to 273.0 K (still ice), the average number of strong hydrogen bonds (SHBs, rOO ≤ 2.93 Å) decreases from 4.0 to 3.3, but upon melting at 273.5 K, the number of SHBs drops suddenly to 2.3, decreasing slowly to 2.1 at 298 K and 1.6 at 400 K. The lifetime of the SHBs is 90.3 fs at 298 K, increasing monotonically for lower temperature. These SHBs connect to form multibranched polymer chains (151 H2O per chain at 298 K), where branch points have 3 SHBs and termination points have 1 SHB. This dynamic fluctuating branched polymer view of water provides a dramatically modified paradigm for understanding the properties of water. It may explain the 20-nm angular correlation lengths at 298 K and the critical point at 227 K in supercooled water. Indeed, the 15% jump in themore » SHB lifetime at 227 K suggests that the supercooled critical point may correspond to a phase transition temperature of the dynamic polymer structure. This paradigm for water could have a significant impact on the properties for protein, DNA, and other materials in aqueous media.« less

Authors:
ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Electricity (OE), Advanced Grid Research & Development. Power Systems Engineering Research; USDOE Office of Science (SC)
OSTI Identifier:
1492085
Alternate Identifier(s):
OSTI ID: 1610790
Grant/Contract Number:  
SC0004993; SC0014607
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: 116 Journal Issue: 6; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Science & Technology - Other Topics; water structure; molecular dynamics; liquid–liquid critical point; radial distribution function; density-functional theory

Citation Formats

Naserifar, Saber, and Goddard, III, William A. Liquid water is a dynamic polydisperse branched polymer. United States: N. p., 2019. Web. https://doi.org/10.1073/pnas.1817383116.
Naserifar, Saber, & Goddard, III, William A. Liquid water is a dynamic polydisperse branched polymer. United States. https://doi.org/10.1073/pnas.1817383116
Naserifar, Saber, and Goddard, III, William A. Thu . "Liquid water is a dynamic polydisperse branched polymer". United States. https://doi.org/10.1073/pnas.1817383116.
@article{osti_1492085,
title = {Liquid water is a dynamic polydisperse branched polymer},
author = {Naserifar, Saber and Goddard, III, William A.},
abstractNote = {We developed the RexPoN force field for water based entirely on quantum mechanics. It predicts the properties of water extremely accurately, withTmelt= 273.3 K (273.15 K) and properties at 298 K: ΔHvap= 10.36 kcal/mol (10.52), density = 0.9965 g/cm3 (0.9965), entropy = 68.4 J/mol/K (69.9), and dielectric constant = 76.1 (78.4), where experimental values are in parentheses. Upon heating from 0.0 K (ice) to 273.0 K (still ice), the average number of strong hydrogen bonds (SHBs, rOO ≤ 2.93 Å) decreases from 4.0 to 3.3, but upon melting at 273.5 K, the number of SHBs drops suddenly to 2.3, decreasing slowly to 2.1 at 298 K and 1.6 at 400 K. The lifetime of the SHBs is 90.3 fs at 298 K, increasing monotonically for lower temperature. These SHBs connect to form multibranched polymer chains (151 H2O per chain at 298 K), where branch points have 3 SHBs and termination points have 1 SHB. This dynamic fluctuating branched polymer view of water provides a dramatically modified paradigm for understanding the properties of water. It may explain the 20-nm angular correlation lengths at 298 K and the critical point at 227 K in supercooled water. Indeed, the 15% jump in the SHB lifetime at 227 K suggests that the supercooled critical point may correspond to a phase transition temperature of the dynamic polymer structure. This paradigm for water could have a significant impact on the properties for protein, DNA, and other materials in aqueous media.},
doi = {10.1073/pnas.1817383116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 116,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1817383116

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Cited by: 11 works
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