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Analyzing the errors of DFT approximations for compressed water systems

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4885440· OSTI ID:1565181
 [1];  [2];  [2];  [3]
  1. Univ. College London (UCL), London (United Kingdom). Dept. of Earth Sciences; Univ. College London (UCL), London (United Kingdom). London Centre for Nanotechnology; Univ. College London (UCL), London (United Kingdom). Thomas Young Center; Univ. College London (UCL), London (United Kingdom). Dept. of Physics and Astronomy
  2. Univ. of Cambridge, Cambridge (United Kingdom). Dept. of Engineering
  3. Univ. College London (UCL), London (United Kingdom). London Centre for Nanotechnology; Univ. College London (UCL), London (United Kingdom). Thomas Young Center; Univ. College London (UCL), London (United Kingdom). Dept. of Physics and Astronomy
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In this work, we report an extensive study of the errors of density functional theory (DFT) approximations for compressed water systems. The approximations studied are based on the widely used PBE and BLYP exchange-correlation functionals, and we characterize their errors before and after correction for 1- and 2-body errors, the corrections being performed using the methods of Gaussian approximation potentials. The errors of the uncorrected and corrected approximations are investigated for two related types of water system: first, the compressed liquid at temperature 420 K and density 1.245 g/cm3 where the experimental pressure is 15 kilobars; second, thermal samples of compressed water clusters from the trimer to the 27-mer. For the liquid, we report four first-principles molecular dynamics simulations, two generated with the uncorrected PBE and BLYP approximations and a further two with their 1- and 2-body corrected counterparts. The errors of the simulations are characterized by comparing with experimental data for the pressure, with neutron-diffraction data for the three radial distribution functions, and with quantum Monte Carlo (QMC) benchmarks for the energies of sets of configurations of the liquid in periodic boundary conditions. The DFT errors of the configuration samples of compressed water clusters are computed using QMC benchmarks. We find that the 2-body and beyond-2-body errors in the liquid are closely related to similar errors exhibited by the clusters. For both the liquid and the clusters, beyond-2-body errors of DFT make a substantial contribution to the overall errors, so that correction for 1- and 2-body errors does not suffice to give a satisfactory description. For BLYP, a recent representation of 3-body energies due to Medders, Babin, and Paesani [J. Chem. Theory Comput. 9, 1103 (2013)] gives a reasonably good way of correcting for beyond-2-body errors, after which the remaining errors are typically 0.5 mEh ≃ 15 meV/monomer for the liquid and the clusters.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1565181
Alternate ID(s):
OSTI ID: 22308740
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 141; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Toward ab initio molecular dynamics modeling for sum-frequency generation spectra; an efficient algorithm based on surface-specific velocity-velocity correlation function journal September 2015
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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

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