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Title: On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4824481· OSTI ID:1565167
 [1];  [2];  [3];  [4];  [5];  [5];  [6];  [3]
  1. Fritz Haber Inst. of the Max Planck Society, Berlin (Germany); Princeton Univ., NJ (United States)
  2. Univ. of Vienna (Austria)
  3. Fritz Haber Inst. of the Max Planck Society, Berlin (Germany)
  4. Univ. College London, Kings Cross (United Kingdom); Univ. College London, Bloomsbury (United Kingdom)
  5. Univ. College London, Kings Cross (United Kingdom)
  6. Princeton Univ., NJ (United States)
+ Show Author Affiliations

Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [B. Santra, J. Klimeš, D. Alfè, A. Tkatchenko, B. Slater, A. Michaelides, R. Car, and M. Scheffler, Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.

Research Organization:
Princeton Univ., NJ (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC)
Grant/Contract Number:
SC0008626
OSTI ID:
1565167
Journal Information:
Journal of Chemical Physics, Vol. 139, Issue 15; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 112 works
Citation information provided by
Web of Science

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Interactions of adsorbed CO2 on water ice at low temperatures journal January 2014
The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water journal August 2014
Molecular reordering processes on ice (0001) surfaces from long timescale simulations journal December 2014
Benchmarking DFT and semiempirical methods on structures and lattice energies for ten ice polymorphs journal March 2015
Probing the structural and dynamical properties of liquid water with models including non-local electron correlation journal August 2015
Computational phase diagrams of noble gas hydrates under pressure journal October 2015
Vibrational renormalisation of the electronic band gap in hexagonal and cubic ice journal December 2015
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Novel phases and superconductivity of tin sulfide compounds journal May 2018
Novel phases in ammonia-water mixtures under pressure journal December 2018
Importance of zero-point energy for crystalline ice phases: A comparison of force fields and density functional theory journal June 2019
On a new nitrogen s X hydrate from ice XVII journal September 2019
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Ab initio theory and modeling of water journal September 2017
SAFT-γ force field for the simulation of molecular fluids: 4. A single-site coarse-grained model of water applicable over a wide temperature range journal March 2015
Evidence for stable square ice from quantum Monte Carlo journal December 2016
Clathrate ice sL: a new crystalline phase of ice with ultralow density predicted by first-principles phase diagram computations journal January 2018
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Consistent structures and interactions by density functional theory with small atomic orbital basis sets journal August 2015
Structural, electronic, and dynamical properties of liquid water by ab initio molecular dynamics based on SCAN functional within the canonical ensemble journal April 2018
High-temperature superconductivity in alkaline and rare earth polyhydrides at high pressure: A theoretical perspective journal February 2019
Structural and spectroscopic features of proton hydrates in the crystalline state. Solid-state DFT study on HCl and triflic acid hydrates journal September 2017
Vibrational renormalisation of the electronic band gap in hexagonal and cubic ice. text January 2015
Perspective: How good is DFT for water? journal April 2016
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Probing the structural and dynamical properties of liquid water with models including non-local electron correlation text January 2015
A new approach to estimate atomic energies journal November 2019
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Structural and spectroscopic features of proton hydrates in the crystalline state. Solid-state DFT study on HCl and triflic acid hydrates text January 2017
Interactions of adsorbed CO$_2$ on water ice at low temperatures text January 2014
Ab initio theory and modeling of water text January 2017
Interaction between water and carbon nanostructures: How good are current density functional approximations? preprint January 2019

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