Van der Waals Density Functional for General Geometries

Van der Waals Density Functional for General Geometries

30 January 2004 | M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist
A van der Waals density functional (vdW-DF) is proposed for general geometries to account for long-range van der Waals forces in density functional theory (DFT). The method extends previous work on layered systems and includes nonlocal correlations through a density-density interaction formula. The functional is expressed in terms of a parametrized kernel, with parameters determined by local density and its gradient. The nonlocal correlation energy is approximated by expanding the long-range part of the correlation functional to second order in a chosen quantity, leading to a density-density interaction formula. This approach allows for a seamless treatment of van der Waals forces alongside other interactions. The method is applied to rare gas and benzene dimers, showing promising results. The correlation energy is divided into two parts: a local-density approximation (LDA) for the short-range part and a nonlocal part treated in the full potential approximation (FPA). The nonlocal part is derived from an expression involving the density response function and the dielectric function. The functional is evaluated using a plane-wave representation, with an approximate form for the kernel $ \phi $ derived from the long-range part of the correlation functional. The method is tested against experimental data for Ar and Kr dimers, showing good agreement with experimental binding energies and distances. For benzene dimers, the method highlights the importance of using the revPBE exchange functional to avoid erroneous attraction in exchange-only calculations. The results demonstrate the effectiveness of the vdW-DF method for sparse systems, including van der Waals complexes and biomolecules, where traditional local and semilocal functionals fail. The method is expected to be useful for calculating properties of large van der Waals bound molecules that are too complex for wavefunction-based methods. The work is supported by grants from the Swedish Foundation for Strategic Research and the Swedish Scientific Council.A van der Waals density functional (vdW-DF) is proposed for general geometries to account for long-range van der Waals forces in density functional theory (DFT). The method extends previous work on layered systems and includes nonlocal correlations through a density-density interaction formula. The functional is expressed in terms of a parametrized kernel, with parameters determined by local density and its gradient. The nonlocal correlation energy is approximated by expanding the long-range part of the correlation functional to second order in a chosen quantity, leading to a density-density interaction formula. This approach allows for a seamless treatment of van der Waals forces alongside other interactions. The method is applied to rare gas and benzene dimers, showing promising results. The correlation energy is divided into two parts: a local-density approximation (LDA) for the short-range part and a nonlocal part treated in the full potential approximation (FPA). The nonlocal part is derived from an expression involving the density response function and the dielectric function. The functional is evaluated using a plane-wave representation, with an approximate form for the kernel $ \phi $ derived from the long-range part of the correlation functional. The method is tested against experimental data for Ar and Kr dimers, showing good agreement with experimental binding energies and distances. For benzene dimers, the method highlights the importance of using the revPBE exchange functional to avoid erroneous attraction in exchange-only calculations. The results demonstrate the effectiveness of the vdW-DF method for sparse systems, including van der Waals complexes and biomolecules, where traditional local and semilocal functionals fail. The method is expected to be useful for calculating properties of large van der Waals bound molecules that are too complex for wavefunction-based methods. The work is supported by grants from the Swedish Foundation for Strategic Research and the Swedish Scientific Council.
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Understanding van der Waals density functional for general geometries.