Theoretical investigations concerning the formation of hydrogen bonds in both homomeric, (HCN) n , and heteromeric clusters of the type (HCN) n OHF (n ϭ 1, 2, and 3) have been performed through ab initio molecular orbital calculations at the second-order Møller-Plesset (MP2) and density functional theory (DFT)/B3LYP levels, with the 6-311ϩϩG(d,p) basis set. The formation of hydrogen bonds is investigated in terms of changes in structural, electronic, and vibrational parameters of the free species. Important parameters include the increment in the distance of the HF proton donor species, the increment in the HC distance of HCN moiety, and the amount of intermolecular charge transfer between the HCN species in the (HCN) n group. It is interesting to point out the different behavior in the HC distance as HCN acts simultaneously as a proton acceptor, proton donor, and a proton donor and acceptor. Other important results concern the cooperative effect (CE) in terms of the stabilization energy and dipole moment. Both CEs increase with cluster size and are more pronounced for the heteroclusters. The HF stretching frequency is red-shifted on going in the direction (HCN)OHF 3 (HCN) 2 OHF 3 (HCN) 3 OHF. This trend is in
A theoretical investigation about the cooperative effect on ( HCN )n homo and ( HCN )n ⋯ HF heterochains was performed in terms of structural parameters and topological properties obtained in concordance with the protocol of Bader's atoms in molecules theory. Initially, the hydrogen bonding distances, electronic densities, and Laplacian descriptors were used to characterize small ( HCN )n and ( HCN )n ⋯ HF chains formed by n = 2–4 units of HCN . Hydrogen bond distances and distribution of charge density have revealed that the cooperative effect on ( HCN )n ⋯ HF heterochains is ruled by the polarity of the extreme hydrofluoric acid species. Furthermore, we investigated larger homo and heterochain systems formed by n = 2–8 molecules of HCN . In this insight, the drastic polarized effect caused by HF molecule which was considered very substantial at prior, in fact is seriously limited by an excessive number of HCN molecules connected to the heterochain. This leads to a stabilization of the ( N ⋯ HF ) hydrogen bonds with invariable electronic density in the range of [Formula: see text]. In this stage and henceforth, the cooperative effect is re-established with n = 4 molecules of HCN . Thereby, the electronic density of the hydrogen bonds become unaltered within the ( HCN )n ⋯ HF heterochains.
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.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.