Symmetry‐adapted perturbation theory based on density functional theory for noncovalent interactions

The combination of symmetry‐adapted perturbation theory (SAPT) of intermolecular interactions with a density functional theory (DFT) description of the underlying molecular properties, known as DFT‐SAPT or SAPT(DFT), is reviewed, with a focus on methodology. A theoretical formalism avoiding an overlap expansion and the single‐exchange approximation for the second‐order exchange contributions is presented, and ways to include higher order contributions are discussed. The influence of the exchange‐correlation potential and kernel underlying any DFT‐SAPT calculation will be explicated. Enhancements of the computational efficiency through density fitting are described and comparisons to coupled cluster theory and experiment benchmark the performance of the method.

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