Role of Exchange in Density Functional Theory for Weakly-Interacting Systems: Quantum Monte Carlo Analysis of Electron Density and Interaction Energy

2009/03/01 by Yosuke Kanai, Jeffrey C. Grossman, J. N. Grossman
Chemical Engineering · Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Catalysis and Oxidation Reactions #Density functional theory #Diffusion Monte Carlo #Exchange interaction #Hybrid functional #Local-density approximation #Markov chain Monte Carlo #Mathematics #Monte Carlo method #Monte Carlo molecular modeling #Nuclear magnetic resonance #Orbital-free density functional theory #Physics #Quantum #Quantum Monte Carlo #Quantum mechanics #Quantum, superfluid, helium dynamics #Reptation #Spectroscopy and Quantum Chemical Studies #Statistical physics #Time-dependent density functional theory #cond-mat.mtrl-sci #cond-mat.other

paper · pdf · doi:10.1103/physreva.80.032504

6 Pages, 3 figures, In press at Phys. Rev. A

openalex publication_date 2009/03/01 · arxiv created 2009/09/12 · arxiv updated 2015/05/14 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/05

Abstract

We analyze the density-functional theory (DFT) description of weak interactions by employing diffusion and reptation quantum Monte Carlo (QMC) calculations, for a set of benzene-molecule complexes. While the binding energies depend significantly on the exchange-correlation approximation employed for DFT calculations, QMC calculations show that the electron density is accurately described within DFT, including the quantitative features in the reduced density gradient. We elucidate how the enhancement of the exchange-energy density at a large reduced density gradient plays a critical role in obtaining accurate DFT description of weakly interacting systems.

Citations

• Generalized Gradient Approximation Made Simple
• Van der Waals Density Functional for General Geometries
• General atomic and molecular electronic structure system
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Density-functional approximation for the correlation energy of the inhomogeneous electron gas
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
• Evidence for van der Waals adhesion in gecko setae
• Prescription for the design and selection of density functional approximations: More constraint satisfaction with fewer fits
• 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
• Self-Consistent Equations Including Exchange and Correlation Effects
• Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation