title: 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.
authors: Department of Chemistry, Institute of Physical and Theoretical Chemistry, University of Graz, Heinrichstraße 28/IV, 8010 Graz (Austria); Department of Chemistry, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476 Potsdam (Germany). Adrian_Daniel.Boese@uni-graz.at.
authors: A Daniel
authors: AD
authors: Boese
mesh_terms: D000641:Ammonia / Q000737:chemistry; D019281:Dimerization; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000641:Ammonia; D006859:Hydrogen
keywords: ab initio calculations; basis sets; density functional calculations; hydrogen bonds; intermolecular interactions