Theoretical Evaluation of the Molecular Inclusion Process between Chlordecone and Cyclodextrins: A New Method for Mitigating the Basis Set Superposition Error in the Case of an Implicit Solvation Model

Abstract

The aim of this work is to describe the molecular inclusion of chlordecone with α-, β-, and γ-cyclodextrin in aqueous solution using quantum mechanics. The guest–host complexes of chlordecone and cyclodextrins are modeled in aqueous solution using the multiple minima hypersurface methodology with a PM6-D3H4X semiempirical Hamiltonian, and the lowest energy minima obtained are reoptimized using the M06-2X density functional and the intermolecular interactions described using quantum theory of atoms in molecules (QTAIM). The studied complexes are classified according to the degree of inclusion, namely, total occlusion, partial occlusion, and external interaction. More stable complexes are obtained when γ-CD is used as the host molecule. The interactions characterized through QTAIM analysis are all of electrostatic nature, predominantly of dispersive type. In this work, a method based on the counterpoise correction is also discussed to mitigate the basis set superposition error in density functional theory calculations when using an implicit solvation model.

Role of Basic Surface Groups of Activated Carbon in Chlordecone and β-Hexachlorocyclohexane Adsorption: A Molecular Modelling Study

“…Although Gibbs's free energy of association (∆G ASSOC ) is the thermodynamic criteria used to define the spontaneity of a process, the association energy (∆E ASSOC ) was used in this study. This criterion has been profusely used by previous researchers [22,23,29,30,34,35,39,40] since it is computationally simpler compared to ∆G, and it avoids having to calculate the association entropies. It is defined as ∆E ASSOC = E supermolecule − E ref , where E supermolecule is the energy of the formed molecular complex by the activated carbon model (with and without SGs) and the interacting in the studied system molecules (in this case: CLD, β-HCH, and water molecules) and E ref is the energy of the isolated molecules.…”

“…Previously, molecular modeling studies of chlordecone and metaldehyde interactions with acidic activated carbon surface functional groups have been published using this methodology [24,29,30]. The present methodology was also used to theoretically evaluate the molecular inclusion process between CLD and cyclodextrins [34]. In addition, Jáuregui-Haza et al [35], studied the guest-host complexes of 1-iodochlordecone and β-1-iodopentachlorocyclohexane with cyclodextrins to use them as radiotracers of organochlorine pesticides in polluted water.…”

Zinc and Its Critical Role in Retinitis pigmentosa: Insights from DFT/SMD Calculations

“…The effect of the surrounding medium is accounted for by applying the B3LYP calculations in combination with the solvation model based on density (SMD) continuum dielectric model at the same level of theory. A dielectric constant ε = 4 is used to mimic an active site deeply buried in the protein matrix, while an ε of ∼30 corresponds to a partially solvent-exposed one. − The application of this particular solvation model excludes the necessity of the basis set superposition error (BSSE) correction as pointed out in ref . Charges on the Zn 2+ cations were calculated by two different schemes: full Natural Bond Orbital (NBO) Analysis and a procedure using the charge density distribution–Hirshfeld technique …”

Complexation of trivalent metal cations (Al3+, Ga3+, In3+, La3+, Lu3+) to cucurbiturils: a DFT/SMD evaluation of the key factors governing the host–guest recognition

“…BSSE correction was not applied to any of the host-guest constructs studied at e = 78. 31 All DFT calculations were performed using the Gaussian 09 computational chemistry software package. 29 The PyMOL molecular graphics system was used to generate the molecular graphics images.…”