Density functional theory augmented with an empirical dispersion term. Interaction energies and geometries of 80 noncovalent complexes compared with ab initio quantum mechanics calculations

2006/12/21 by Petr Jurečka, Jiří Černý, Pavel Hobza +1 · 2 citations
Biochemistry, Genetics and Molecular Biology · Chemistry · Physics and Astronomy · Mathematics · #DNA and Nucleic Acid Chemistry #Crystallography and molecular interactions #Advanced Chemical Physics Studies #Basis set #Density functional theory #van der Waals force #Ab initio #Dispersion (optics) #Wave function #Chemistry #Scaling #London dispersion force #Computational chemistry #Linear scale #Function (biology) #Statistical physics #Molecular physics #Quantum mechanics #Physics #Mathematics #Molecule #Geometry

paper · doi:10.1002/jcc.20570

openalex publication_date 2006/12/21 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28

Abstract

Standard density functional theory (DFT) is augmented with a damped empirical dispersion term. The damping function is optimized on a small, well balanced set of 22 van der Waals (vdW) complexes and verified on a validation set of 58 vdW complexes. Both sets contain biologically relevant molecules such as nucleic acid bases. Results are in remarkable agreement with reference high-level wave function data based on the CCSD(T) method. The geometries obtained by full gradient optimization are in very good agreement with the best available theoretical reference. In terms of the standard deviation and average errors, results including the empirical dispersion term are clearly superior to all pure density functionals investigated-B-LYP, B3-LYP, PBE, TPSS, TPSSh, and BH-LYP-and even surpass the MP2/cc-pVTZ method. The combination of empirical dispersion with the TPSS functional performs remarkably well. The most critical part of the empirical dispersion approach is the damping function. The damping parameters should be optimized for each density functional/basis set combination separately. To keep the method simple, we optimized mainly a single factor, s(R), scaling globally the vdW radii. For good results, a basis set of at least triple-zeta quality is required and diffuse functions are recommended, since the basis set superposition error seriously deteriorates the results. On average, the dispersion contribution to the interaction energy missing in the DFT functionals examined here is about 15 and 100% for the hydrogen-bonded and stacked complexes considered, respectively.

Citations

• Generalized Gradient Approximation Made Simple
• Van der Waals Density Functional for General Geometries
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Electronic structure calculations on workstation computers: The program system turbomole
• van der Waals Volumes and Radii
• Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
• Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
• Optimization of Effective Atom Centered Potentials for London Dispersion Forces in Density Functional Theory
• Dispersion corrections to density functionals for water aromatic interactions
• Unexpectedly Strong Energy Stabilization Inside the Hydrophobic Core of Small Protein Rubredoxin Mediated by Aromatic Residues: Correlated Ab Initio Quantum Chemical Calculations
• The role of the basis set: Assessing density functional theory
• Accurate description of van der Waals complexes by density functional theory including empirical corrections
• Density-functional thermochemistry. III. The role of exact exchange
• The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
• Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F

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