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  4. Structure and dynamics of liquid water from ab initio simulations: adding Minnesota density functionals to Jacob's ladder
 
research article

Structure and dynamics of liquid water from ab initio simulations: adding Minnesota density functionals to Jacob's ladder

Villard, Justin  
•
Bircher, Martin P.
•
Rothlisberger, Ursula  
February 15, 2024
Chemical Science

The accurate representation of the structural and dynamical properties of water is essential for simulating the unique behavior of this ubiquitous solvent. Here we assess the current status of describing liquid water using ab initio molecular dynamics, with a special focus on the performance of all the later generation Minnesota functionals. Findings are contextualized within the current knowledge on DFT for describing bulk water under ambient conditions and compared to experimental data. We find that, contrary to the prevalent idea that local and semilocal functionals overstructure water and underestimate dynamical properties, M06-L, revM06-L, and M11-L understructure water, while MN12-L and MN15-L overdistance water molecules due to weak cohesive effects. This can be attributed to a weakening of the hydrogen bond network, which leads to dynamical fingerprints that are over fast. While most of the hybrid Minnesota functionals (M06, M08-HX, M08-SO, M11, MN12-SX, and MN15) also yield understructured water, their dynamical properties generally improve over their semilocal counterparts. It emerges that exact exchange is a crucial component for accurately describing hydrogen bonds, which ultimately leads to corrections in both the dynamical and structural properties. However, an excessive amount of exact exchange strengthens hydrogen bonds and causes overstructuring and slow dynamics (M06-HF). As a compromise, M06-2X is the best performing Minnesota functional for water, and its D3 corrected variant shows very good structural agreement. From previous studies considering nuclear quantum effects (NQEs), the hybrid revPBE0-D3, and the rung-5 RPA (RPA@PBE) have been identified as the only two approximations that closely agree with experiments. Our results suggest that the M06-2X(-D3) functionals have the potential to further improve the reproduction of experimental properties when incorporating NQEs through path integral approaches. This work provides further proof that accurate modeling of water interactions requires the inclusion of both exact exchange and balanced (non-local) correlation, highlighting the need for higher rungs on Jacob's ladder to achieve predictive simulations of complex biological systems in aqueous environments.

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Type
research article
DOI
10.1039/d3sc05828j
Web of Science ID

WOS:001166657500001

Author(s)
Villard, Justin  
Bircher, Martin P.
Rothlisberger, Ursula  
Date Issued

2024-02-15

Publisher

Royal Soc Chemistry

Published in
Chemical Science
Subjects

Physical Sciences

•

Der-Waals Interactions

•

Random-Phase-Approximation

•

Main-Group Thermochemistry

•

Molecular-Dynamics

•

Self-Diffusion

•

Noncovalent Interactions

•

Temperature-Dependence

•

Collective Description

•

Electron Interactions

•

Computational Chemistry

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
ISIC  
LCBC  
FunderGrant Number

Schweizerischer Nationalfonds zur Frderung der Wissenschaftlichen Forschung

200020_185092

Swiss National Science Foundation

NCCR MUST

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Available on Infoscience
March 18, 2024
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/206464
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