Density Functional Theory and Hydrogen Bonds: Are We There Yet?

Abstract Density functional theory (DFT) has become more successful at introducing dispersion interactions, and can be thus applied to a wide range of systems. Amongst these are systems that contain hydrogen bonds, which are extremely important for the biological regime. Here, the description of hydrogen‐bonded interactions by DFT with and without dispersion corrections is investigated. For small complexes, for which electrostatics are the determining factor in the intermolecular interactions, the inclusion of dispersion with most functionals yields large errors. Only for larger systems, in which van der Waals interactions are more important, do dispersion corrections improve the performance of DFT for hydrogen‐bonded systems. None of the studied functionals, including double hybrid functionals (with the exception of DSD‐PBEP86 without dispersion corrections), are more accurate than MP2 for the investigated species.