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.

Hydrogen-bonded complexes upon spatial confinement: structural and energetic aspects

“…Due to their simplicity and versatility some of them have been intensively investigated as the model complexes for the cooperative effect analysis, [101][102][103] topological and energetic property calculations 94,104,105 as well as in the field of nonlinear optics. [106][107][108][109][110] In the scope of present study the linearity of all of the investigated systems has been assumed. It should be noted that only for the HCNÁ Á ÁHCN and HCNÁ Á ÁHCCH complexes the linear structures have been experimentally observed.…”

“…Such an approach has been previously used in various theoretical studies in which properties of the linear HFÁ Á ÁHF complexes were considered. 94,105,[107][108][109][110] In order to get a deeper insight into the nature of the selected complexes as well as to distinguish differences among them, the decomposition of the interaction energy in vacuum, according to the variational-perturbational scheme, has been conducted. From the data reported in Table 1 one can notice that for all investigated complexes the electrostatic contribution to DE is the most significant.…”

Understanding Stability Trends along the Lanthanide Series

“…Basis-set superposition errors (BSSEs), which are an undesirable consequence of using finite basis sets that leads to an overestimation of the binding energy, were calculated using the standard Counterpoise method [37] with calculations performed in the gas phase. [38] Table 1. Parameterized PCM radii and ionic radii [Å] for Ln 3+ ions and comparison of experimental and calculated hydration free energies [kcal mol −1 ].…”

H4octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)

“…Basis set superposition errors (BSSEs), which represent an undesirable consequence of using finite basis sets that leads to an overestimation of the binding energy, were calculated using the standard counterpoise method 43 with calculations performed in the gas phase. 44 The NMR shielding tensors of the [Zn(octapa)] 2− system were calculated in aqueous solution at the TPSSh/TZVP level by using the GIAO method. 45 For 13 C NMR chemical shift calculation purposes, the NMR shielding tensors of tetramethylsilane (TMS) were calculated at the same level.…”