Quantifying the intrinsic strength of C–H⋯O intermolecular interactions

0572517 - ÚMCH 2024 RIV CH eng J - Článek v odborném periodiku
Czernek, Jiří - Brus, Jiří - Czerneková, Vladimíra - Kobera, Libor
Quantifying the intrinsic strength of C–H⋯O intermolecular interactions.
Molecules. Roč. 28, č. 11 (2023), č. článku 4478. E-ISSN 1420-3049
Grant CEP: GA ČR(CZ) GA22-03187S
Výzkumná infrastruktura: e-INFRA CZ - 90140
Institucionální podpora: RVO:61389013 ; RVO:68378271
Klíčová slova: hydrogen bonding * noncovalent interactions * CCSD(T)
Obor OECD: Polymer science; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)
Impakt faktor: 4.6, rok: 2022
Způsob publikování: Open access
https://www.mdpi.com/1420-3049/28/11/4478

It has been recognized that the C–H⋯O structural motif can be present in destabilizing as well as highly stabilizing intermolecular environments. Thus, it should be of interest to describe the strength of the C–H⋯O hydrogen bond for constant structural factors so that this intrinsic strength can be quantified and compared to other types of interactions. This description is provided here for C2h-symmetric dimers of acrylic acid by means of the calculations that employ the coupled-cluster theory with singles, doubles, and perturbative triples [CCSD(T)] together with an extrapolation to the complete basis set (CBS) limit. Dimers featuring the C–H⋯O and O–H⋯O hydrogens bonds are carefully investigated in a wide range of intermolecular separations by the CCSD(T)/CBS approach, and also by the symmetry-adapted perturbation theory (SAPT) method, which is based on the density-functional theory (DFT) treatment of monomers. While the nature of these two types of hydrogen bonding is very similar according to the SAPT-DFT/CBS calculations and on the basis of a comparison of the intermolecular potential curves, the intrinsic strength of the C–H⋯O interaction is found to be about a quarter of its O–H⋯O counterpart that is less than one might anticipate.

Trvalý link: https://hdl.handle.net/11104/0343664