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Title: The Quest for Accurate Liquid Water Properties from First Principles

Journal Article · · Journal of Physical Chemistry Letters
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States)
  2. Charles Univ., Prague (Czech Republic)
  3. Stanford Univ., Stanford, CA (United States)
+ Show Author Affiliations

Developing accurate ab initio molecular dynamics (AIMD) models that capture both electronic reorganization and nuclear quantum effects associated with hydrogen bonding is key to quantitative understanding of bulk water and its anomalies as well as its role as a universal solvent. For condensed phase simulations, AIMD has typically relied on the generalized gradient approximation (GGA) of density functional theory (DFT) as the underlying model chemistry for the potential energy surface, with nuclear quantum effects (NQEs) sometimes modeled by performing classical molecular dynamics simulations at elevated temperatures. Here we show that the properties of liquid water obtained from the meta-GGA B97M-rV functional, when evaluated using accelerated path integral molecular dynamics simulations, display accuracy comparable to a computationally expensive dispersion-corrected hybrid functional, revPBE0-D3. We show that the meta-GGA DFT functional reproduces bulk water properties including radial distribution functions, self-diffusion coefficients, and infrared spectra with comparable accuracy of a much more expensive hybrid functional. This work demonstrates that the underlying quality of a good DFT functional requires evaluation with quantum nuclei and that high-temperature simulations are a poor proxy for properly treating NQEs.

Research Organization:
Stanford Univ., CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0014437; AC02-05CH11231
OSTI ID:
1527093
Alternate ID(s):
OSTI ID: 1542312
Journal Information:
Journal of Physical Chemistry Letters, Vol. 9, Issue 17; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

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Cited By (12)

Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold journal January 2020
Low-order many-body interactions determine the local structure of liquid water journal January 2019
Quantum kinetic energy and isotope fractionation in aqueous ionic solutions journal January 2020
Ab initio spectroscopy of water under electric fields journal January 2019
Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder journal January 2020
Recent advances in quantum‐mechanical molecular dynamics simulations of proton transfer mechanism in various water‐based environments journal May 2019
Ensemble first-principles molecular dynamics simulations of water using the SCAN meta-GGA density functional journal October 2019
Interaction between water and carbon nanostructures: How good are current density functional approximations? journal October 2019
Electrostatic decoupling of periodic images of plane‐wave‐expanded densities and derived atomic point charges journal November 1995
Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder text January 2020
Interaction between water and carbon nanostructures: How good are current density functional approximations? preprint January 2019
Interplay of Water and a Supramolecular Capsule for Catalysis of Reductive Elimination Reaction from Gold preprint January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY