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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, with T melt = 273.3 K (273.15 K) and properties at 298 K: ΔH vap = 10.36 kcal/mol (10.52), density = 0.9965 g/cm 3 (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, r OO ≤ 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 H 2 O 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 atmore » 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.« less

Authors:
ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE Office of Electricity Delivery and Energy Reliability (OE), Power Systems Engineering Research and Development (R&D) (OE-10)
OSTI Identifier:
1492085
Grant/Contract Number:  
SC0004993
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:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Naserifar, Saber, and Goddard, III, William A. Liquid water is a dynamic polydisperse branched polymer. United States: N. p., 2019. Web. doi:10.1073/pnas.1817383116.
Naserifar, Saber, & Goddard, III, William A. Liquid water is a dynamic polydisperse branched polymer. United States. doi:10.1073/pnas.1817383116.
Naserifar, Saber, and Goddard, III, William A. Thu . "Liquid water is a dynamic polydisperse branched polymer". United States. doi: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, with T melt = 273.3 K (273.15 K) and properties at 298 K: ΔH vap = 10.36 kcal/mol (10.52), density = 0.9965 g/cm 3 (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, r OO ≤ 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 H 2 O 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
DOI: 10.1073/pnas.1817383116

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Works referenced in this record:

Antifreeze proteins govern the precipitation of trehalose in a freezing-avoiding insect at low temperature
journal, May 2016

  • Wen, Xin; Wang, Sen; Duman, John G.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 24
  • DOI: 10.1073/pnas.1601519113

Ab initio theory and modeling of water
journal, September 2017

  • Chen, Mohan; Ko, Hsin-Yu; Remsing, Richard C.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 41
  • DOI: 10.1073/pnas.1712499114

“Tetrahedrality” and the Relationship between Collective Structure and Radial Distribution Functions in Liquid Water
journal, May 2007

  • Mason, P. E.; Brady, J. W.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 20
  • DOI: 10.1021/jp068581n

Salt-induced Long-to-Short Range Orientational Transition in Water
journal, June 2018


Energetics of Hydrogen Bond Network Rearrangements in Liquid Water
journal, October 2004


Metastable liquid–liquid transition in a molecular model of water
journal, June 2014

  • Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang
  • Nature, Vol. 510, Issue 7505
  • DOI: 10.1038/nature13405

The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water
journal, August 2014

  • DiStasio, Robert A.; Santra, Biswajit; Li, Zhaofeng
  • The Journal of Chemical Physics, Vol. 141, Issue 8
  • DOI: 10.1063/1.4893377

Predictions of the Properties of Water from First Principles
journal, March 2007


Simulating water with rigid non-polarizable models: a general perspective
journal, January 2011

  • Vega, Carlos; Abascal, Jose L. F.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 44
  • DOI: 10.1039/c1cp22168j

Extension of the Polarizable Charge Equilibration Model to Higher Oxidation States with Applications to Ge, As, Se, Br, Sn, Sb, Te, I, Pb, Bi, Po, and At Elements
journal, November 2017

  • Oppenheim, Julius J.; Naserifar, Saber; Goddard, William A.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpca.7b06612

Phase behaviour of metastable water
journal, November 1992

  • Poole, Peter H.; Sciortino, Francesco; Essmann, Ulrich
  • Nature, Vol. 360, Issue 6402
  • DOI: 10.1038/360324a0

Note: Assessment of the SCAN+rVV10 functional for the structure of liquid water
journal, December 2017

  • Wiktor, Julia; Ambrosio, Francesco; Pasquarello, Alfredo
  • The Journal of Chemical Physics, Vol. 147, Issue 21
  • DOI: 10.1063/1.5006146

Polarizable charge equilibration model for predicting accurate electrostatic interactions in molecules and solids
journal, March 2017

  • Naserifar, Saber; Brooks, Daniel J.; Goddard, William A.
  • The Journal of Chemical Physics, Vol. 146, Issue 12
  • DOI: 10.1063/1.4978891

The Structure of the First Coordination Shell in Liquid Water
journal, May 2004


On the absolute thermodynamics of water from computer simulations: A comparison of first-principles molecular dynamics, reactive and empirical force fields
journal, December 2012

  • Pascal, Tod A.; Schärf, Daniel; Jung, Yousung
  • The Journal of Chemical Physics, Vol. 137, Issue 24
  • DOI: 10.1063/1.4771974

On the phase diagram of water with density functional theory potentials: The melting temperature of ice Ih with the Perdew–Burke–Ernzerhof and Becke–Lee–Yang–Parr functionals
journal, June 2009

  • Yoo, Soohaeng; Zeng, Xiao Cheng; Xantheas, Sotiris S.
  • The Journal of Chemical Physics, Vol. 130, Issue 22
  • DOI: 10.1063/1.3153871

A flexible model for water based on TIP4P/2005
journal, December 2011

  • González, Miguel A.; Abascal, José L. F.
  • The Journal of Chemical Physics, Vol. 135, Issue 22
  • DOI: 10.1063/1.3663219

Isobaric−Isothermal Molecular Dynamics Simulations Utilizing Density Functional Theory: An Assessment of the Structure and Density of Water at Near-Ambient Conditions
journal, September 2009

  • Schmidt, Jochen; VandeVondele, Joost; Kuo, I. -F. William
  • The Journal of Physical Chemistry B, Vol. 113, Issue 35
  • DOI: 10.1021/jp901990u

Efficient Quantum Monte Carlo Energies for Molecular Dynamics Simulations
journal, February 2005


Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure
journal, November 2007

  • Bergmann, Uwe; Di Cicco, Andrea; Wernet, Philippe
  • The Journal of Chemical Physics, Vol. 127, Issue 17
  • DOI: 10.1063/1.2784123

Modelling Water: A Lifetime Enigma
journal, March 2015

  • Ouyang, John F.; Bettens, Ryan P. A.
  • CHIMIA International Journal for Chemistry, Vol. 69, Issue 3
  • DOI: 10.2533/chimia.2015.104

Accurate ab initio and “hybrid” potential energy surfaces, intramolecular vibrational energies, and classical ir spectrum of the water dimer
journal, April 2009

  • Shank, Alex; Wang, Yimin; Kaledin, Alexey
  • The Journal of Chemical Physics, Vol. 130, Issue 14
  • DOI: 10.1063/1.3112403

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

  • Skinner, Lawrie B.; Huang, Congcong; Schlesinger, Daniel
  • The Journal of Chemical Physics, Vol. 138, Issue 7
  • DOI: 10.1063/1.4790861

Maxima in the thermodynamic response and correlation functions of deeply supercooled water
journal, December 2017


Mechanisms Underlying the Mpemba Effect in Water from Molecular Dynamics Simulations
journal, February 2015

  • Jin, Jaehyeok; Goddard, William A.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 5
  • DOI: 10.1021/jp511752n

Structure and Dynamics of the TIP3P, SPC, and SPC/E Water Models at 298 K
journal, November 2001

  • Mark, Pekka; Nilsson, Lennart
  • The Journal of Physical Chemistry A, Vol. 105, Issue 43
  • DOI: 10.1021/jp003020w

The quantum mechanics-based polarizable force field for water simulations
journal, November 2018

  • Naserifar, Saber; Goddard, William A.
  • The Journal of Chemical Physics, Vol. 149, Issue 17
  • DOI: 10.1063/1.5042658

Structure, Dynamics, and Spectral Diffusion of Water from First-Principles Molecular Dynamics
journal, September 2014

  • Bankura, Arindam; Karmakar, Anwesa; Carnevale, Vincenzo
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp506120t

Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells
journal, January 2017

  • Cheng, Tao; Goddard, William A.; An, Qi
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 4
  • DOI: 10.1039/C6CP08055C

Atom Pair Distribution Functions of Liquid Water at 25 C from Neutron Diffraction
journal, September 1982


The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038

Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0
journal, November 2015

  • Cheng, Tao; Xiao, Hai; Goddard, William A.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02247

Structure and dynamics of aqueous solutions from PBE-based first-principles molecular dynamics simulations
journal, October 2016

  • Pham, Tuan Anh; Ogitsu, Tadashi; Lau, Edmond Y.
  • The Journal of Chemical Physics, Vol. 145, Issue 15
  • DOI: 10.1063/1.4964865