A density functional theory approach to noncovalent interactions via interacting monomer densities.
A recently proposed "DFT + dispersion" treatment (Rajchel et al., Phys. Rev. Lett., 2010, 104, 163001) is described in detail and illustrated by more examples. The formalism derives the dispersion-free density functional theory (DFT) interaction energy and combines it with the dispersion energy from separate DFT calculations. It consists of the self-consistent polarization of DFT monomers restrained by the exclusion principle via the Pauli blockade technique. Within the monomers a complete exchange-correlation potential should be used, but between them only the exact exchange operates. The application to a wide range of molecular complexes from rare-gas dimers to hydrogen-bonds to π-electron interactions shows good agreement with benchmark values.
Rajchel
Łukasz
Ł
Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477, USA. lrajchel@tiger.chem.uw.edu.pl
Żuchowski
Piotr S
PS
Hapka
Michał
M
Modrzejewski
Marcin
M
Szczęśniak
Małgorzata M
MM
Chałasiński
Grzegorz
G
D019281:Dimerization; D006860:Hydrogen Bonding; D005741:Noble Gases / Q000737:chemistry; D011789:Quantum Theory
D005741:Noble Gases