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research article

Ab initio thermodynamics of liquid and solid water

Cheng, Bingqing  
•
Engel, Edgar A.  
•
Behler, Joerg
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January 22, 2019
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)

Thermodynamic properties of liquid water as well as hexagonal (Ih) and cubic (Ic) ice are predicted based on density functional theory at the hybrid-functional level, rigorously taking into account quantum nuclear motion, anharmonic fluctuations, and proton disorder. This is made possible by combining advanced free-energy methods and state-of-the-art machine-learning techniques. The ab initio description leads to structural properties in excellent agreement with experiments and reliable estimates of the melting points of light and heavy water. We observe that nuclear-quantum effects contribute a crucial 0.2 meV/H2O to the stability of ice Ih, making it more stable than ice Ic. Our computational approach is general and transferable, providing a comprehensive framework for quantitative predictions of ab initio thermodynamic properties using machine-learning potentials as an intermediate step.

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Type
research article
DOI
10.1073/pnas.1815117116
Web of Science ID

WOS:000456336100009

Author(s)
Cheng, Bingqing  
•
Engel, Edgar A.  
•
Behler, Joerg
•
Dellago, Christoph
•
Ceriotti, Michele  
Date Issued

2019-01-22

Publisher

National Academy of Sciences

Published in
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)
Volume

116

Issue

4

Start page

1110

End page

1115

Subjects

Multidisciplinary Sciences

•

Science & Technology - Other Topics

•

ab initio thermodynamics

•

machine-learning potential

•

water

•

density functional theory

•

nuclear quantum effects

•

van-der-waals

•

stacking disorder

•

cubic ice

•

nuclear

•

density

•

dynamics

•

model

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
February 1, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/154294
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