Optimal finite-range atomic basis sets for liquid water and ice

Abstract

Finite-range numerical atomic orbitals are the basis functions of choice for several first principles methods, due to their flexibility and scalability. Generating and testing such basis sets, however, remains a significant challenge for the end user. We discuss these issues and present a new scheme for generating improved polarization orbitals of finite range. We then develop a series of high-accuracy basis sets for the water molecule, and report on their performance in describing the monomer and dimer, two phases of ice, and liquid water at ambient and high density. The tests are performed by comparison with plane-wave calculations, and show the atomic orbital basis sets to exhibit an excellent level of transferability and consistency. The highest-order bases (quadruple-zeta) are shown to give accuracies comparable to a plane-wave kinetic energy cutoff of at least ~1000 eV for quantities such as energy differences and ionic forces, as well as achieving significantly greater accuracies for total energies and absolute pressures.

17 pages, 14 figures

References in corpus (2)

• On how good DFT exchange-correlation functionals are for H bonds in small water clusters: Benchmarks approaching the complete basis set limit
• Room temperature compressibility and diffusivity of liquid water from first principles

Cited by in corpus (19)

• 2D ice from first principles: structures and phase transitions
• The PSML format and library for norm-conserving pseudopotential data curation and interoperability
• Polar meron-antimeron networks in strained and twisted bilayers
• Structural and configurational properties of nanoconfined monolayer ice from first principles
• Room temperature compressibility and diffusivity of liquid water from first principles
• Nanoplasmonics simulations at the basis set limit through completeness-optimized, local numerical basis sets
• Theory of polar domains in moiré heterostructures
• Atomic electronic structure calculations with Hermite interpolating polynomials
• Optimization of an exchange-correlation density functional for water
• The orbital minimization method for electronic structure calculations with finite-range atomic basis sets
• Electronic and Nuclear Quantum Effects on the Ice XI/Ice Ih Phase Transition
• Flexoelectric radial polarization of single-walled nanotubes from first-principles
• Performance analysis of electronic structure codes on HPC systems: A case study of SIESTA
• Role of Water Model on Ion Dissociation at Ambient Conditions
• Redefining the dielectric response of nanoconfined liquids: insights from water
• Complexity Reduction in Density Functional Theory: Locality in Space and Energy
• Atomic Confinement Potentials and the Generation of Numerical Atomic Orbitals
• Importance profiles. Visualization of atomic basis set requirements
• The effect of magnetism and temperature on the stability of Cr, V, Al carbide MAX phases