Towards an assessment of the accuracy of density functional theory for first principles simulations of water II

Abstract

A series of 20 ps ab initio molecular dynamic simulations of water at ambient density and temperatures ranging from 300 to 450K are presented. Both Car-Parrinello (CP) and Born-Oppenheimer (BO) molecular dynamics techniques are compared for systems containing 54 and 64 water molecules. At 300K, excellent agreement is found between radial distribution functions (RDFs) obtained with BO and CP dynamics, provided an appropriately small value of the fictitious mass parameter is used in the CP simulation. However, we find that the diffusion coefficients computed from CP dynamics are approximately two times larger than the corresponding BO simulations for T>400K, where statistically meaningful comparisons can be made. Overall, both BO and CP dynamics at 300 K yield overstructured RDFs and slow diffusion as compared to experiment. In order to understand these discrepancies, the effect of proton quantum motion is considered with the use of empirical interaction potentials. We find strong evidence that proton quantum effects may have a larger impact than previously thought on structure and diffusion of the liquid.

Final version, accepted for publication in JCP

References in corpus (3)

• Free energy of liquid water on the basis of quasi-chemical theory and ab initio molecular dynamics
• How well do Car-Parrinello simulations reproduce the Born-Oppenheimer surface ? Theory and Examples
• A first principles simulation of rigid water

Cited by in corpus (37)

• Perspective: How good is DFT for water?
• The Individual and Collective Effects of Exact Exchange and Dispersion Interactions on the Ab Initio Structure of Liquid Water
• Density, structure and dynamics of water: the effect of Van der Waals interactions
• Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries
• Network equilibration and first-principles liquid water
• Time-reversible Born-Oppenheimer molecular dynamics
• Cobalt-Porphyrin Catalyzed Electrochemical Reduction of Carbon Dioxide in Water II: Mechanism from First Principles
• On the Accuracy of van der Waals Inclusive Density-Functional Theory Exchange-Correlation Functionals for Ice at Ambient and High Pressures
• Ab initio molecular dynamics calculations of ion hydration free energies
• A unified electrostatic and cavitation model for first-principles molecular dynamics in solution
• The electronic structure of liquid water within density functional theory
• Local Structure Analysis in $Ab$ $Initio$ Liquid Water
• Structural, Electronic, and Dynamical Properties of Liquid Water by ab initio Molecular Dynamics based on SCAN Functional within the Canonical Ensemble
• Towards First Principles prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries
• Heat transport in liquid water from first-principles and deep-neural-network simulations
• Energy benchmarks for water clusters and ice structures from an embedded many-body expansion
• Coupled cluster benchmarks of water monomers and dimers extracted from DFT liquid water: the importance of monomer deformations
• Ab-initio molecular dynamics simulation of liquid water by Quantum Monte Carlo
• Persistence of Covalent Bonding in Liquid Silicon Probed by Inelastic X-ray Scattering
• A fundamental mechanism for carbon-film lubricity identified by means of ab initio molecular dynamics
• On the theory underlying the Car-Parrinello method and the role of the fictitious mass parameter
• Viscosity in water from first-principles and deep-neural-network simulations
• A Systematic Study of Chloride Ion Solvation in Water using van der Waals Inclusive Hybrid Density Functional Theory
• vdW-DF Study of energetic, structural, and vibrational properties of small water clusters and ice Ih
• The random phase approximation applied to ice
• Hydrogen bonding and coordination in normal and supercritical water from X-ray inelastic scattering
• On "the complete basis set limit" and plane-wave methods in first-principles simulations of water
• Novel structural features of CDK inhibition revealed by an ab initio computational method combined with dynamic simulations
• Thermodynamics of water modeled using ab initio simulations
• A Quantum-Mechanics Molecular-Mechanics scheme for extended systems
• Ab initio molecular dynamics study of manganese porphine hydration and interaction with nitric oxide
• X-ray absorption of liquid water by advanced ab initio methods
• First Principles Determination of the Potential-of-Zero-Charge in an Alumina-coated Aluminum/Water Interface Model for Corrosion Applications
• Electronic structure of water from Koopmans-compliant functionals
• Molecular Biology at the Quantum Level: Can Modern Density Functional Theory Forge the Path?
• Structural characterizations of water-metal interfaces
• Monte Carlo Simulation for Spheres with Two Length Scales