Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data

2009/02/20 by Alexandre Tkatchenko, Matthias Scheffler · 11 citations
Physics and Astronomy · Chemistry · #Advanced Chemical Physics Studies #Quantum, superfluid, helium dynamics #Fullerene Chemistry and Applications #van der Waals force #Van der Waals radius #Intermolecular force #Van der Waals surface #Atom (system on chip) #Physics #Atomic physics #Van der Waals strain #Electron density #Density functional theory #Molecule #Ground state #Electron #Molecular physics #Quantum mechanics

paper · pdf · doi:10.1103/physrevlett.102.073005

openalex publication_date 2009/02/20 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

We present a parameter-free method for an accurate determination of long-range van der Waals interactions from mean-field electronic structure calculations. Our method relies on the summation of interatomic C6 coefficients, derived from the electron density of a molecule or solid and accurate reference data for the free atoms. The mean absolute error in the C6 coefficients is 5.5% when compared to accurate experimental values for 1225 intermolecular pairs, irrespective of the employed exchange-correlation functional. We show that the effective atomic C6 coefficients depend strongly on the bonding environment of an atom in a molecule. Finally, we analyze the van der Waals radii and the damping function in the C6R(-6) correction method for density-functional theory calculations.

Citations

• Van der Waals Density Functional for General Geometries
• The Influence of Retardation on the London-van der Waals Forces
• High-Precision Calculations of Dispersion Coefficients, Static Dipole Polarizabilities, and Atom-Wall Interaction Constants for Alkali-Metal Atoms
• Nonuniversality of the dispersion interaction: analytic benchmarks for van der Waals energy functionals
• van der Waals Volumes and Radii
• Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
• Dispersion corrections to density functionals for water aromatic interactions
• Accurate description of van der Waals complexes by density functional theory including empirical corrections

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• Structural and electronic properties of Li-intercalated graphene on SiC(0001)
• Enhanced piezoelectricity and modified dielectric screening of two-dimensional group-IV monochalcogenides
• Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation
• Molecular force fields with gradient-domain machine learning (GDML): Comparison and synergies with classical force fields
• Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions
• Density functional theory [wikipedia]

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