Signatures of a liquid–liquid transition in an ab initio deep neural network model for water
Abstract
The possible existence of a metastable liquid–liquid transition (LLT) and a corresponding liquid–liquid critical point (LLCP) in supercooled liquid water remains a topic of much debate. An LLT has been rigorously proved in three empirically parametrized molecular models of water, and evidence consistent with an LLT has been reported for several other such models. In contrast, experimental proof of this phenomenon has been elusive due to rapid ice nucleation under deeply supercooled conditions. In this work, we combined density functional theory (DFT), machine learning, and molecular simulations to shed additional light on the possible existence of an LLT in water. We trained a deep neural network (DNN) model to represent the ab initio potential energy surface of water from DFT calculations using the Strongly Constrained and Appropriately Normed (SCAN) functional. We then used advanced sampling simulations in the multithermal–multibaric ensemble to efficiently explore the thermophysical properties of the DNN model. The simulation results are consistent with the existence of an LLCP, although they do not constitute a rigorous proof thereof. We fit the simulation data to a two-state equation of state to provide an estimate of the LLCP’s location. These combined results—obtained from a purely first-principles approach with no empiricalmore »
- Authors:
-
- Department of Chemistry, Princeton University, Princeton, NJ 08544,
- Program in Applied and Computational Mathematics, Princeton University, Princeton, NJ 08544,
- Department of Chemistry, Princeton University, Princeton, NJ 08544,, Program in Applied and Computational Mathematics, Princeton University, Princeton, NJ 08544,, Department of Physics, Princeton University, Princeton, NJ 08544,, Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, NJ 08544,
- Princeton Institute for the Science and Technology of Materials, Princeton University, Princeton, NJ 08544,, Department of Chemical and Biological Engineering, Princeton University, Princeton, NJ 08544
- Department of Chemical and Biological Engineering, Princeton University, Princeton, NJ 08544
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1670208
- Alternate Identifier(s):
- OSTI ID: 1853194; OSTI ID: 1999129
- Grant/Contract Number:
- SC001934; SC0019394
- 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: 117 Journal Issue: 42; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 36 MATERIALS SCIENCE; Science & Technology - Other Topics; water; liquid–liquid transition; molecular simulations; machine learning
Citation Formats
Gartner, III, Thomas E., Zhang, Linfeng, Piaggi, Pablo M., Car, Roberto, Panagiotopoulos, Athanassios Z., and Debenedetti, Pablo G. Signatures of a liquid–liquid transition in an ab initio deep neural network model for water. United States: N. p., 2020.
Web. doi:10.1073/pnas.2015440117.
Gartner, III, Thomas E., Zhang, Linfeng, Piaggi, Pablo M., Car, Roberto, Panagiotopoulos, Athanassios Z., & Debenedetti, Pablo G. Signatures of a liquid–liquid transition in an ab initio deep neural network model for water. United States. https://doi.org/10.1073/pnas.2015440117
Gartner, III, Thomas E., Zhang, Linfeng, Piaggi, Pablo M., Car, Roberto, Panagiotopoulos, Athanassios Z., and Debenedetti, Pablo G. Fri .
"Signatures of a liquid–liquid transition in an ab initio deep neural network model for water". United States. https://doi.org/10.1073/pnas.2015440117.
@article{osti_1670208,
title = {Signatures of a liquid–liquid transition in an ab initio deep neural network model for water},
author = {Gartner, III, Thomas E. and Zhang, Linfeng and Piaggi, Pablo M. and Car, Roberto and Panagiotopoulos, Athanassios Z. and Debenedetti, Pablo G.},
abstractNote = {The possible existence of a metastable liquid–liquid transition (LLT) and a corresponding liquid–liquid critical point (LLCP) in supercooled liquid water remains a topic of much debate. An LLT has been rigorously proved in three empirically parametrized molecular models of water, and evidence consistent with an LLT has been reported for several other such models. In contrast, experimental proof of this phenomenon has been elusive due to rapid ice nucleation under deeply supercooled conditions. In this work, we combined density functional theory (DFT), machine learning, and molecular simulations to shed additional light on the possible existence of an LLT in water. We trained a deep neural network (DNN) model to represent the ab initio potential energy surface of water from DFT calculations using the Strongly Constrained and Appropriately Normed (SCAN) functional. We then used advanced sampling simulations in the multithermal–multibaric ensemble to efficiently explore the thermophysical properties of the DNN model. The simulation results are consistent with the existence of an LLCP, although they do not constitute a rigorous proof thereof. We fit the simulation data to a two-state equation of state to provide an estimate of the LLCP’s location. These combined results—obtained from a purely first-principles approach with no empirical parameters—are strongly suggestive of the existence of an LLT, bolstering the hypothesis that water can separate into two distinct liquid forms.},
doi = {10.1073/pnas.2015440117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 42,
volume = 117,
place = {United States},
year = {Fri Oct 02 00:00:00 EDT 2020},
month = {Fri Oct 02 00:00:00 EDT 2020}
}
https://doi.org/10.1073/pnas.2015440117
Works referenced in this record:
Perspective: Crossing the Widom line in no man’s land: Experiments, simulations, and the location of the liquid-liquid critical point in supercooled water
journal, October 2018
- Hestand, Nicholas J.; Skinner, J. L.
- The Journal of Chemical Physics, Vol. 149, Issue 14
Comment on “Maxima in the thermodynamic response and correlation functions of deeply supercooled water”
journal, May 2018
- Caupin, Frédéric; Holten, Vincent; Qiu, Chen
- Science, Vol. 360, Issue 6390
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
Relation between the Widom line and the dynamic crossover in systems with a liquid-liquid phase transition
journal, November 2005
- Xu, L.; Kumar, P.; Buldyrev, S. V.
- Proceedings of the National Academy of Sciences, Vol. 102, Issue 46
Physics of the Liquid-Liquid Critical Point
journal, October 2003
- Sciortino, Francesco; La Nave, Emilia; Tartaglia, Piero
- Physical Review Letters, Vol. 91, Issue 15
Ab initio thermodynamics of liquid and solid water
journal, January 2019
- Cheng, Bingqing; Engel, Edgar A.; Behler, Jörg
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 4
Phase behaviour of metastable water
journal, November 1992
- Poole, Peter H.; Sciortino, Francesco; Essmann, Ulrich
- Nature, Vol. 360, Issue 6402
Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man’s land
journal, November 2017
- Handle, Philip H.; Loerting, Thomas; Sciortino, Francesco
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 51
Machine Learning for Molecular Simulation
journal, April 2020
- Noé, Frank; Tkatchenko, Alexandre; Müller, Klaus-Robert
- Annual Review of Physical Chemistry, Vol. 71, Issue 1
Nature of the anomalies in the supercooled liquid state of the mW model of water
journal, May 2013
- Holten, Vincent; Limmer, David T.; Molinero, Valeria
- The Journal of Chemical Physics, Vol. 138, Issue 17
The liquid–liquid transition in supercooled ST2 water: a comparison between umbrella sampling and well-tempered metadynamics
journal, January 2013
- Palmer, Jeremy C.; Car, Roberto; Debenedetti, Pablo G.
- Faraday Discussions, Vol. 167
The phase diagram of water from quantum simulations
journal, January 2012
- McBride, Carl; Noya, Eva G.; Aragones, Juan L.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 29
Water Modeled As an Intermediate Element between Carbon and Silicon †
journal, April 2009
- Molinero, Valeria; Moore, Emily B.
- The Journal of Physical Chemistry B, Vol. 113, Issue 13
Reparametrized E3B (Explicit Three-Body) Water Model Using the TIP4P/2005 Model as a Reference
journal, April 2015
- Tainter, Craig J.; Shi, Liang; Skinner, James L.
- Journal of Chemical Theory and Computation, Vol. 11, Issue 5
Molecular dynamics simulations in the multibaric–multithermal ensemble
journal, June 2004
- Okumura, Hisashi; Okamoto, Yuko
- Chemical Physics Letters, Vol. 391, Issue 4-6
Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water
journal, April 2016
- Singh, Rakesh S.; Biddle, John W.; Debenedetti, Pablo G.
- The Journal of Chemical Physics, Vol. 144, Issue 14
Isothermal compressibility of supercooled water and evidence for a thermodynamic singularity at −45°C
journal, August 1976
- Speedy, R. J.; Angell, C. A.
- The Journal of Chemical Physics, Vol. 65, Issue 3
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Equation of state of supercooled water simulated using the extended simple point charge intermolecular potential
journal, November 1997
- Harrington, Stephen; Poole, Peter H.; Sciortino, Francesco
- The Journal of Chemical Physics, Vol. 107, Issue 18
Multithermal-Multibaric Molecular Simulations from a Variational Principle
journal, February 2019
- Piaggi, Pablo M.; Parrinello, Michele
- Physical Review Letters, Vol. 122, Issue 5
Water: A Tale of Two Liquids
journal, April 2016
- Gallo, Paola; Amann-Winkel, Katrin; Angell, Charles Austen
- Chemical Reviews, Vol. 116, Issue 13
Temperature dependence of nuclear quantum effects on liquid water via artificial neural network model based on SCAN meta-GGA functional
journal, July 2020
- Yao, Yi; Kanai, Yosuke
- The Journal of Chemical Physics, Vol. 153, Issue 4
Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges
journal, April 2016
- Ceriotti, Michele; Fang, Wei; Kusalik, Peter G.
- Chemical Reviews, Vol. 116, Issue 13
Variational Approach to Enhanced Sampling and Free Energy Calculations
journal, August 2014
- Valsson, Omar; Parrinello, Michele
- Physical Review Letters, Vol. 113, Issue 9
Water-like anomalies as a function of tetrahedrality
journal, March 2018
- Russo, John; Akahane, Kenji; Tanaka, Hajime
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 15
DeePMD-kit: A deep learning package for many-body potential energy representation and molecular dynamics
journal, July 2018
- Wang, Han; Zhang, Linfeng; Han, Jiequn
- Computer Physics Communications, Vol. 228
Structural transformation in supercooled water controls the crystallization rate of ice
journal, November 2011
- Moore, Emily B.; Molinero, Valeria
- Nature, Vol. 479, Issue 7374
PLUMED 2: New feathers for an old bird
journal, February 2014
- Tribello, Gareth A.; Bonomi, Massimiliano; Branduardi, Davide
- Computer Physics Communications, Vol. 185, Issue 2
Generalization of the Wang-Landau method for off-lattice simulations
journal, November 2002
- Shell, M. Scott; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z.
- Physical Review E, Vol. 66, Issue 5
Two-structure thermodynamics for the TIP4P/2005 model of water covering supercooled and deeply stretched regions
journal, January 2017
- Biddle, John W.; Singh, Rakesh S.; Sparano, Evan M.
- The Journal of Chemical Physics, Vol. 146, Issue 3
On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice
journal, November 2016
- Reddy, Sandeep K.; Straight, Shelby C.; Bajaj, Pushp
- The Journal of Chemical Physics, Vol. 145, Issue 19
Stability-limit conjecture. An interpretation of the properties of water
journal, March 1982
- Speedy, Robin J.
- The Journal of Physical Chemistry, Vol. 86, Issue 6
The structural validity of various thermodynamical models of supercooled water
journal, October 2016
- Pathak, H.; Palmer, J. C.; Schlesinger, D.
- The Journal of Chemical Physics, Vol. 145, Issue 13
Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985
- Car, R.; Parrinello, M.
- Physical Review Letters, Vol. 55, Issue 22
Supercooled and glassy water
journal, October 2003
- Debenedetti, Pablo G.
- Journal of Physics: Condensed Matter, Vol. 15, Issue 45
Developing ab initio quality force fields from condensed phase quantum-mechanics/molecular-mechanics calculations through the adaptive force matching method
journal, August 2008
- Akin-Ojo, Omololu; Song, Yang; Wang, Feng
- The Journal of Chemical Physics, Vol. 129, Issue 6
Deep Potential: A General Representation of a Many-Body Potential Energy Surface
journal, January 2018
- Han, Jiequn; Zhang, Linfeng; Car, Roberto
- Communications in Computational Physics, Vol. 23, Issue 3
Understanding water’s anomalies with locally favoured structures
journal, April 2014
- Russo, John; Tanaka, Hajime
- Nature Communications, Vol. 5, Issue 1
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
Nanoscale Dynamics of Phase Flipping in Water near its Hypothesized Liquid-Liquid Critical Point
journal, June 2012
- Kesselring, T. A.; Franzese, G.; Buldyrev, S. V.
- Scientific Reports, Vol. 2, Issue 1
Advances in Computational Studies of the Liquid–Liquid Transition in Water and Water-Like Models
journal, August 2018
- Palmer, Jeremy C.; Poole, Peter H.; Sciortino, Francesco
- Chemical Reviews, Vol. 118, Issue 18
Simple physical model of liquid water
journal, January 2000
- Tanaka, Hajime
- The Journal of Chemical Physics, Vol. 112, Issue 2
Entropy-driven liquid–liquid separation in supercooled water
journal, October 2012
- Holten, V.; Anisimov, M. A.
- Scientific Reports, Vol. 2, Issue 1
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
A potential model for the study of ices and amorphous water: TIP4P/Ice
journal, June 2005
- Abascal, J. L. F.; Sanz, E.; García Fernández, R.
- The Journal of Chemical Physics, Vol. 122, Issue 23
Direct Evidence in the Scattering Function for the Coexistence of Two Types of Local Structures in Liquid Water
journal, January 2020
- Shi, Rui; Tanaka, Hajime
- Journal of the American Chemical Society, Vol. 142, Issue 6
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Evidence for a liquid-liquid critical point in supercooled water within the E3B3 model and a possible interpretation of the kink in the homogeneous nucleation line
journal, June 2016
- Ni, Yicun; Skinner, J. L.
- The Journal of Chemical Physics, Vol. 144, Issue 21
How van der Waals interactions determine the unique properties of water
journal, July 2016
- Morawietz, Tobias; Singraber, Andreas; Dellago, Christoph
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 30
Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature
journal, June 2014
- Sellberg, J. A.; Huang, C.; McQueen, T. A.
- Nature, Vol. 510, Issue 7505
Improved simulation of liquid water by molecular dynamics
journal, February 1974
- Stillinger, Frank H.; Rahman, Aneesur
- The Journal of Chemical Physics, Vol. 60, Issue 4
Liquid water is a dynamic polydisperse branched polymer
journal, January 2019
- Naserifar, Saber; Goddard, William A.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 6
Equation of State for Supercooled Water at Pressures up to 400 MPa
journal, December 2014
- Holten, Vincent; Sengers, Jan V.; Anisimov, Mikhail A.
- Journal of Physical and Chemical Reference Data, Vol. 43, Issue 4
Widom line and the liquid–liquid critical point for the TIP4P/2005 water model
journal, December 2010
- Abascal, José L. F.; Vega, Carlos
- The Journal of Chemical Physics, Vol. 133, Issue 23
Anomalies in Supercooled Water at ∼230 K Arise from a 1D Polymer to 2D Network Topological Transformation
journal, September 2019
- Naserifar, Saber; Goddard, William A.
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 20
Liquid-liquid transition in supercooled water suggested by microsecond simulations
journal, July 2013
- Li, Y.; Li, J.; Wang, F.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 30
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DP-GEN: A concurrent learning platform for the generation of reliable deep learning based potential energy models
journal, February 2020
- Zhang, Yuzhi; Wang, Haidi; Chen, Weijie
- Computer Physics Communications
Generalized Neural-Network Representation of High-Dimensional Potential-Energy Surfaces
journal, April 2007
- Behler, Jörg; Parrinello, Michele
- Physical Review Letters, Vol. 98, Issue 14
The relationship between liquid, supercooled and glassy water
journal, November 1998
- Mishima, Osamu; Stanley, H. Eugene
- Nature, Vol. 396, Issue 6709
A general purpose model for the condensed phases of water: TIP4P/2005
journal, December 2005
- Abascal, J. L. F.; Vega, C.
- The Journal of Chemical Physics, Vol. 123, Issue 23
Response to Comment on “Maxima in the thermodynamic response and correlation functions of deeply supercooled water”
journal, May 2018
- Kim, Kyung Hwan; Späh, Alexander; Pathak, Harshad
- Science, Vol. 360, Issue 6390
Equation of state of water based on the SCAN meta-GGA density functional
journal, January 2020
- Zhao, Gang; Shi, Shuyi; Xie, Huijuan
- Physical Chemistry Chemical Physics, Vol. 22, Issue 8
Singularity-free interpretation of the thermodynamics of supercooled water
journal, June 1996
- Sastry, Srikanth; Debenedetti, Pablo G.; Sciortino, Francesco
- Physical Review E, Vol. 53, Issue 6
Liquid-liquid transition in ST2 water
journal, December 2012
- Liu, Yang; Palmer, Jeremy C.; Panagiotopoulos, Athanassios Z.
- The Journal of Chemical Physics, Vol. 137, Issue 21
Maxima in the thermodynamic response and correlation functions of deeply supercooled water
journal, December 2017
- Kim, Kyung Hwan; Späh, Alexander; Pathak, Harshad
- Science, Vol. 358, Issue 6370
Study of the ST2 model of water close to the liquid–liquid critical point
journal, January 2011
- Sciortino, Francesco; Saika-Voivod, Ivan; Poole, Peter H.
- Physical Chemistry Chemical Physics, Vol. 13, Issue 44
Second critical point in two realistic models of water
journal, July 2020
- Debenedetti, Pablo G.; Sciortino, Francesco; Zerze, Gül H.
- Science, Vol. 369, Issue 6501
Modeling Molecular Interactions in Water: From Pairwise to Many-Body Potential Energy Functions
journal, May 2016
- Cisneros, Gerardo Andrés; Wikfeldt, Kjartan Thor; Ojamäe, Lars
- Chemical Reviews, Vol. 116, Issue 13
Density anomaly of water at negative pressures from first principles
journal, June 2018
- Singraber, Andreas; Morawietz, Tobias; Behler, Jörg
- Journal of Physics: Condensed Matter, Vol. 30, Issue 25
Active learning of uniformly accurate interatomic potentials for materials simulation
journal, February 2019
- Zhang, Linfeng; Lin, De-Ye; Wang, Han
- Physical Review Materials, Vol. 3, Issue 2
Two-state thermodynamics of the ST2 model for supercooled water
journal, March 2014
- Holten, Vincent; Palmer, Jeremy C.; Poole, Peter H.
- The Journal of Chemical Physics, Vol. 140, Issue 10
A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model
journal, August 2016
- González, Miguel A.; Valeriani, Chantal; Caupin, Frédéric
- The Journal of Chemical Physics, Vol. 145, Issue 5
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
Systematic Improvement of a Classical Molecular Model of Water
journal, August 2013
- Wang, Lee-Ping; Head-Gordon, Teresa; Ponder, Jay W.
- The Journal of Physical Chemistry B, Vol. 117, Issue 34