title: On the calculations of interaction energies and induced electric properties within the polarizable continuum model.
abstract: In this work we investigate the influence of a polarizable environment on the interaction energies and the interaction-induced (excess) static electric dipole properties for the selected model hydrogen-bonded complexes. The excess properties were estimated for water and hydrogen fluoride dimers using the supermolecular approach and assuming the polarizable continuum model (PCM) as a representation of the polarizable environment. We analyze in this context the performance of the counterpoise correction and the consequences of various possible monomer cavity choices. The polarizable environment reduces the absolute magnitudes of interaction energies and interaction-induced dipole moments, whereas an increase is observed for the absolute magnitudes of induced polarizabilities and first hyperpolarizabilities. Our results indicate that the use of either monomeric (MC) or dimeric (DC) cavities in calculations of monomer properties does not change qualitatively the resultant excess properties. We conclude that the DC scheme is more consistent with the definition of the interaction energy and consequently also the interaction-induced property, whereas the MC scheme corresponds to the definition of stabilization energy. Our results indicate also a good performance of the counterpoise correction scheme for the self-consistent methods in the case of all studied properties.
authors.affiliation: Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Chemistry Department, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Zawada
authors.forename: Robert W
authors.initials: RW
authors.lastname: Góra
authors.forename: Mikołaj M
authors.initials: MM
authors.lastname: Mikołajczyk
authors.forename: Wojciech
authors.initials: W
authors.lastname: Bartkowiak
mesh_terms: D004583:Electrons; D006858:Hydrofluoric Acid / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D006858:Hydrofluoric Acid