Association Complexes of Calix[6]arenes with Amino Acids Explained by Energy-Partitioning Methods.

Intermolecular complexes with calixarenes are intriguing because of multiple possibilities of noncovalent binding for both polar and nonpolar molecules, including docking in the calixarene cavity. In this contribution calix[6]arenes interacting with amino acids are studied with an additional aim to show that tools such as symmetry-adapted perturbation theory (SAPT), functional-group SAPT (F-SAPT), and systematic molecular fragmentation (SMF) methods may provide explanations for different numbers of noncovalent bonds and of their varying strength for various calixarene conformers and guest molecules. The partitioning of the interaction energy provides an easy way to identify hydrogen bonds, including those with unconventional hydrogen acceptors, as well as other noncovalent bonds, and to find repulsive destabilizing interactions between functional groups.

Description of Chiral Complexes within Functional-Group Symmetry-Adapted Perturbation Theory-The Case of (S/R)-Carvone with Derivatives of (-)-Menthol.

Symmetry-adapted perturbation theory (SAPT) and functional-group SAPT (F-SAPT) are applied to examine differences in interaction energies of diastereoisomeric complexes of two chiral molecules of natural origin: (/)-carvone with (-)-menthol. The study is extended by including derivatives of menthol with its hydroxy group exchanged by another functional group, thus examining the substituent effect of the interaction and the interaction differences between diastereoisomers. The partitioning of the interaction energy into functional-group components allows one to explain this phenomenon by the mutual cancellation of attractive and repulsive interactions between functional groups.

Influence of the second layer on geometry and spectral properties of doped two-dimensional hexagonal boron nitride.

Influence of the additional layer of hexagonal boron nitride (h-BN) on structure, energetics, and electronic spectra of a layer doped with magnesium, silicon, phosphorus, aluminum, or carbon atoms has been examined by theoretical methods. The h-BN layers are modeled as BN clusters of over thirty atoms with the defect in the center. The calculations show that atom positions undergo some modifications in the presence of the second layer, which in several cases lead to significant changes in electronic spectra, like (i) modifications of the character of some states from local excitation to a partial charge transfer; (ii) redshift of the majority of lowest excitations; (iii) absence or appearance of new states in comparison with the monolayers.

On the applicability of functional-group symmetry-adapted perturbation theory and other partitioning models for chiral recognition - the case of popular drug molecules interacting with chiral phases.

The applicability of symmetry-adapted perturbation theory (SAPT) and functional-group SAPT (F-SAPT) to study chiral recognition is investigated on an example of three popular chiral drug molecules: ibuprofen, norepinephrine, and baclofen, interacting with phenethylamine or proline - two molecules that are often used as chiral phases in chromatography. The comparison of the F-SAPT with the interacting quantum atoms (IQA) approach is also provided. Accurate estimation of energetic differences of the non-covalent intermolecular complexes composed of two chiral molecules is a necessary prerequisite for the possibility of a prediction of the chiral recognition.

Dimerization Behavior of Methyl Chlorophyllide a as the Model of Chlorophyll a in the Presence of Water Molecules-Theoretical Study.

A dimerization of methyl chlorophyllide a molecules and a role of water in stabilization and properties of methyl chlorophyllide a dimers were studied by means of symmetry-adapted perturbation theory (SAPT), functional-group SAPT (F-SAPT), density-functional theory (DFT), and time-dependent DFT approaches. The quantification of various types of interactions, such as π-π stacking, coordinative, and hydrogen bonding by applying the F-SAPT energy decomposition scheme shows the major role of the magnesium atom and the pheophytin macrocycle in the stability of the complex. The examination of interaction energy components with respect to a mutual orientation of monomers and in the presence or absence of water molecules reveals that the dispersion energy is the main binding factor of the interaction, while water molecules tend to weaken the attraction between methyl chlorophyllide a species.

Substituent effects in the so-called cationπ interaction of benzene and its boron-nitrogen doped analogues: overlooked role of σ-skeleton.

Despite massive efforts to pinpoint the substituent effects in the so-called cationπ systems, no consensus has been yet reached on how substituents exercise their effects in the interaction of the aromatic molecule with the metal ion. The π-polarization (the Hunter model) and the direct local effect (the Wheeler-Houk model) are two lines of thought applied to this problem, but the justification of both approaches is based on insufficiently proven assumptions and approximations. In order to shed more light on this issue we propose a new approach which enables us to gauge directly the energetic trends resulting from the interaction of the ring with the cation.

Interaction of Non-polarizable Cations with Azaborine Isomers and Their Mono-Substituted Derivatives: Position, Induction, and Non-Classical Effects Matter.

Progress in BN/CC isosterism has opened an overwhelming urge to find prospective applications of this class of materials. Herein, the interaction of three BN isosteres of benzene, i. e.

Interaction of Boron-Nitrogen Doped Benzene Isomers with Water.

The interaction of 1,2-dihydro-1,2-, 1,3-dihydro-1,3- and 1,4-dihydro-1,4-azaborine isomers with one and two water molecules has been studied using a variety of supermolecular (Møller-Plesset = MP, and coupled cluster = CC) as well as perturbational (symmetry-adapted perturbation theory = SAPT) electron-correlation methods in the complete basis-set limit. It has been found that the water molecule binds to azaborine isomers through O-H···π, π-H···O, and dihydrogen bonding linkages. The SAPT interaction energy decomposition shows that these complexes are mostly stabilized by dispersion followed closely by induction contributions.