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. Various other features can be explained by energy partitioning, such as the red shift of an IR stretching frequency for some hydroxy groups, which arises from their attraction to the phenyl ring of calixarene. Pairs of hydrogen bonds and other noncovalent bonds of similar magnitude found by F-SAPT explain an increase in the stability of both inclusion and outer complexes.
A comprehensive theoretical study of the lowest electronic vertical excitations of the CBCN defect in the monolayer of hexagonal boron nitride has been performed. Both the periodic boundary conditions approach and the finite-cluster simulation of the defect have been utilized at the density-functional theory (DFT) level. Clusters of increasing sizes have been used in order to estimate artefacts resulting from edge effects. The stability of the results with respect to several density functionals and various basis sets has been also examined. High-level ab initio calculations with methods like EOM-CCSD, ADC(2), and TD-CC2, were performed for the smallest clusters. It turns out that TD-DFT with the CAM-B3LYP functional gives similar lowest excitation energies as EOM-CCSD, ADC(2), and TD-CC2. The lowest excitation energies resulting from the periodic-boundary calculation utilizing the Bethe-Salpeter equation are in agreement with the results for finite clusters. The analysis of important configurations and transition densities shows that for all studied methods, the lowest excited state is localized on two carbon atoms and their closest neighbours and has a large dipole transition moment. The optimized geometries for the lowest two excited states indicate that in both cases the carbon-carbon bond becomes a single bond, while for the second excited state additionally one from boron-nitrogen bonds looses its partially double character. The calculation of the excitation energies at the respective optimal geometry reveals that these two energies become about 0.5 eV lower than vertical excitations from the ground-state geometry.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.