Liquid Water through Density-Functional Molecular Dynamics: Plane-Wave vs Atomic-Orbital Basis Sets.

Area of Science:

• Computational chemistry
• Materials science
• Condensed matter physics

Background:

• Accurate simulation of liquid water properties is crucial for understanding chemical and physical processes.
• Density-functional theory (DFT) is a powerful tool for electronic structure calculations.
• Molecular dynamics (MD) simulations are essential for studying the dynamic behavior of systems.

Purpose of the Study:

• To compare structural, dynamical, and electronic properties of liquid water using two different basis sets in DFT-MD simulations.
• To validate the equivalence of plane-wave and atomic-orbital basis sets for simulating liquid water.
• To assess the reliability of these computational approaches for aqueous solutions.

Main Methods:

• Density-functional molecular dynamics (DFT-MD) simulations were performed.
• Nonlocal density functional with van der Waals interactions was employed.
• Plane-wave and atomic-orbital basis sets were used and compared.

Main Results:

• Structural, dynamical, and electronic properties of liquid water were determined.
• Results obtained using plane-wave and atomic-orbital basis sets showed excellent agreement.
• The theoretical scheme consistently determined electronic structure and atomic forces.

Conclusions:

• Plane-wave and atomic-orbital basis set implementations yield equivalent results for liquid water.
• Both basis set approaches can be used interchangeably for studying liquid water and aqueous solutions.
• The findings support the reliability of DFT-MD for accurate simulations of aqueous systems.