10.1021/acs.jpclett.8b02400.s001
Luis Ruiz Pestana
Luis
Ruiz Pestana
Ondrej Marsalek
Ondrej
Marsalek
Thomas E. Markland
Thomas E.
Markland
Teresa Head-Gordon
Teresa
Head-Gordon
The Quest for Accurate Liquid Water Properties from
First Principles
American Chemical Society
2018
meta-GGA B 97M
0-D
reproduces bulk water properties
quantum effects
Accurate Liquid Water Properties
NQE
AIMD
accuracy
DFT
dynamics simulations
model
2018-08-17 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/The_Quest_for_Accurate_Liquid_Water_Properties_from_First_Principles/6990950
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.