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Title: Ab initio theory and modeling of water

Abstract

Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice Ih at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. Furthermore, these successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner.

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1396061
Alternate Identifier(s):
OSTI ID: 1469913
Grant/Contract Number:  
SC0008726; SC0012575
Resource Type:
Journal Article: 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: 114 Journal Issue: 41; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING; catalysis (heterogeneous); solar (photovoltaic); energy storage (including batteries and capacitors); hydrogen and fuel cells; defects; mechanical behavior; materials and chemistry by design; synthesis (novel materials); water; ab initio theory; hydrogen bonding; density functional theory; molecular dynamics

Citation Formats

Chen, Mohan, Ko, Hsin-Yu, Remsing, Richard C., Calegari Andrade, Marcos F., Santra, Biswajit, Sun, Zhaoru, Selloni, Annabella, Car, Roberto, Klein, Michael L., Perdew, John P., and Wu, Xifan. Ab initio theory and modeling of water. United States: N. p., 2017. Web. doi:10.1073/pnas.1712499114.
Chen, Mohan, Ko, Hsin-Yu, Remsing, Richard C., Calegari Andrade, Marcos F., Santra, Biswajit, Sun, Zhaoru, Selloni, Annabella, Car, Roberto, Klein, Michael L., Perdew, John P., & Wu, Xifan. Ab initio theory and modeling of water. United States. doi:10.1073/pnas.1712499114.
Chen, Mohan, Ko, Hsin-Yu, Remsing, Richard C., Calegari Andrade, Marcos F., Santra, Biswajit, Sun, Zhaoru, Selloni, Annabella, Car, Roberto, Klein, Michael L., Perdew, John P., and Wu, Xifan. Mon . "Ab initio theory and modeling of water". United States. doi:10.1073/pnas.1712499114.
@article{osti_1396061,
title = {Ab initio theory and modeling of water},
author = {Chen, Mohan and Ko, Hsin-Yu and Remsing, Richard C. and Calegari Andrade, Marcos F. and Santra, Biswajit and Sun, Zhaoru and Selloni, Annabella and Car, Roberto and Klein, Michael L. and Perdew, John P. and Wu, Xifan},
abstractNote = {Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice Ih at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. Furthermore, these successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner.},
doi = {10.1073/pnas.1712499114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 41,
volume = 114,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1712499114

Citation Metrics:
Cited by: 46 works
Citation information provided by
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Figures / Tables:

Fig. 1 Fig. 1: RDFs (A) gOO(r) and (B) gOH(r) of liquid water predicted by PBE and SCAN at 330 K, as well as that from X-ray diffraction experiments (5) for gOO(r) and joint X-ray/neutron diffraction experiments (4) for gOH(r). An elevated temperature of 30 K was used in AIMD simulations tomore » mimic NQEs (35).« less

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Acceleration schemes for ab initio molecular-dynamics simulations and electronic-structure calculations
journal, October 1994


Maximally localized Wannier functions: Theory and applications
journal, October 2012

  • Marzari, Nicola; Mostofi, Arash A.; Yates, Jonathan R.
  • Reviews of Modern Physics, Vol. 84, Issue 4
  • DOI: 10.1103/RevModPhys.84.1419

Structures of small water clusters using gradient-corrected density functional theory
journal, May 1993


Rotational Motion in Liquid Water Is Anisotropic:  A Nuclear Magnetic Resonance and Molecular Dynamics Simulation Study
journal, August 2001

  • Ropp, J.; Lawrence, C.; Farrar, T. C.
  • Journal of the American Chemical Society, Vol. 123, Issue 33
  • DOI: 10.1021/ja010312h

Pore waters regulate ion permeation in a calcium release-activated calcium channel
journal, October 2013

  • Dong, H.; Fiorin, G.; Carnevale, V.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 43
  • DOI: 10.1073/pnas.1316969110

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Time-Dependent Properties of Liquid Water:  A Comparison of Car−Parrinello and Born−Oppenheimer Molecular Dynamics Simulations
journal, July 2006

  • Kuo, I-Feng W.; Mundy, Christopher J.; McGrath, Matthew J.
  • Journal of Chemical Theory and Computation, Vol. 2, Issue 5
  • DOI: 10.1021/ct6001913

Hydrogen-bond kinetics in liquid water
journal, January 1996

  • Luzar, Alenka; Chandler, David
  • Nature, Vol. 379, Issue 6560
  • DOI: 10.1038/379055a0

Jacob’s ladder of density functional approximations for the exchange-correlation energy
conference, January 2001

  • Perdew, John P.
  • Density functional theory and its application to materials, AIP Conference Proceedings
  • DOI: 10.1063/1.1390175

Water as an Active Constituent in Cell Biology
journal, January 2008


Molecular multipole moments of water molecules in ice Ih
journal, September 1998

  • Batista, Enrique R.; Xantheas, Sotiris S.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 109, Issue 11
  • DOI: 10.1063/1.477058

Norm-Conserving Pseudopotentials
journal, November 1979


Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Density, structure, and dynamics of water: The effect of van der Waals interactions
journal, January 2011

  • Wang, Jue; Román-Pérez, G.; Soler, Jose M.
  • The Journal of Chemical Physics, Vol. 134, Issue 2
  • DOI: 10.1063/1.3521268

Electron distribution in water
journal, June 2000

  • Badyal, Y. S.; Saboungi, M. -L.; Price, D. L.
  • The Journal of Chemical Physics, Vol. 112, Issue 21
  • DOI: 10.1063/1.481541

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

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Ultrafast Hydrogen-Bond Dynamics in the Infrared Spectroscopy of Water
journal, September 2003


Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional
journal, June 2016

  • Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo
  • Nature Chemistry, Vol. 8, Issue 9
  • DOI: 10.1038/nchem.2535

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


Self-diffusion in normal and heavy water in the range 1-45.deg.
journal, March 1973


Crystal Structure and Pair Potentials: A Molecular-Dynamics Study
journal, October 1980


Simulating Fluid-Phase Equilibria of Water from First Principles
journal, January 2006

  • McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 2
  • DOI: 10.1021/jp0535947

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


First-principle-constant pressure molecular dynamics
journal, March 1995

  • Bernasconi, M.; Chiarotti, G. L.; Focher, P.
  • Journal of Physics and Chemistry of Solids, Vol. 56, Issue 3-4
  • DOI: 10.1016/0022-3697(94)00228-2

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

  • Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463940

Dissecting Hydrophobic Hydration and Association
journal, August 2013

  • Remsing, Richard C.; Weeks, John D.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp4053067

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

On the electronic structure of liquid water: Facts and reflections
journal, October 1997


Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation
journal, April 2004

  • Winter, B.; Weber, R.; Widdra, W.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 14
  • DOI: 10.1021/jp030263q

Liquid Water from First Principles:  Investigation of Different Sampling Approaches
journal, August 2004

  • Kuo, I-Feng W.; Mundy, Christopher J.; McGrath, Matthew J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 34
  • DOI: 10.1021/jp047788i

On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures
journal, October 2013

  • Santra, Biswajit; Klimeš, Jiří; Tkatchenko, Alexandre
  • The Journal of Chemical Physics, Vol. 139, Issue 15
  • DOI: 10.1063/1.4824481

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


Water dimer properties in the gradient-corrected density functional theory
journal, June 1992


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Ab initio Electronic Structure of Liquid Water
journal, October 2016


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

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation
journal, August 2015

  • Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost
  • The Journal of Chemical Physics, Vol. 143, Issue 5
  • DOI: 10.1063/1.4927325

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions
journal, January 2015

  • Miceli, Giacomo; de Gironcoli, Stefano; Pasquarello, Alfredo
  • The Journal of Chemical Physics, Vol. 142, Issue 3
  • DOI: 10.1063/1.4905333

Deconstructing Classical Water Models at Interfaces and in Bulk
journal, August 2011

  • Remsing, Richard C.; Rodgers, Jocelyn M.; Weeks, John D.
  • Journal of Statistical Physics, Vol. 145, Issue 2
  • DOI: 10.1007/s10955-011-0299-3

Ground State of the Electron Gas by a Stochastic Method
journal, August 1980


Liquid Water through Density-Functional Molecular Dynamics: Plane-Wave vs Atomic-Orbital Basis Sets
journal, July 2016

  • Miceli, Giacomo; Hutter, Jürg; Pasquarello, Alfredo
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00271

Static and Dynamical Properties of Liquid Water from First Principles by a Novel Car−Parrinello-like Approach
journal, January 2009

  • Kühne, Thomas D.; Krack, Matthias; Parrinello, Michele
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 2
  • DOI: 10.1021/ct800417q

Re-examining the properties of the aqueous vapor–liquid interface using dispersion corrected density functional theory
journal, September 2011

  • Baer, Marcel D.; Mundy, Christopher J.; McGrath, Matthew J.
  • The Journal of Chemical Physics, Vol. 135, Issue 12
  • DOI: 10.1063/1.3633239

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

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Quantum Differences between Heavy and Light Water
journal, August 2008


Density and Compressibility of Liquid Water and Ice from First-Principles Simulations with Hybrid Functionals
journal, July 2015

  • Gaiduk, Alex P.; Gygi, François; Galli, Giulia
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b00901

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

Nuclear quantum effects and hydrogen bond fluctuations in water
journal, September 2013

  • Ceriotti, M.; Cuny, J.; Parrinello, M.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 39
  • DOI: 10.1073/pnas.1308560110

Perspective: How good is DFT for water?
journal, April 2016

  • Gillan, Michael J.; Alfè, Dario; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 144, Issue 13
  • DOI: 10.1063/1.4944633

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