Repozytorium
Wyszukaj
Kolekcje
Inne
Understanding the molecular mechanism of the chlorine atom transfer between ammonia and hypochlorous acid with electron localisation function (ELF).
Autorzy
Rok wydania
2021
Czasopismo
Numer woluminu
119
Strony
e1961035/1-e1961035/12
DOI
10.1080/00268976.2021.1961035
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The nature of the chlorine atom transferred between ammonia and hypochlorous acid was investigated using the bonding evolution theory (BET). The application of topological analysis of electron localisation function (ELF) and Thom's catastrophe theory enabled a detailed description of the evolution of chemical bonds and non-bonding electron density. The BET analysis was performed at the DFT(MN15)/def2-TZVPPD computational level. The Hausdorff distance was used as a qualitative view on the evolution of the ELF field. The molecular mechanism of the chlorination reaction consisted of 11 structural stability domains (SSDs) and 10 ELF catastrophes. Four SSDs were observed before the transition state (TS). The TS was found in SSD V, and six SSDs were distinguished after the TS. The energy barriers were analysed with six different DFT functionals (B3LYP, CAM-B3LYP, LC-ωPBE, M11, MN15, ωB97XD) and def2-TZVPPD basis set. The energy barrier between transition state and reagents was smaller than transition state and products, thus the chlorination of ammonia is thermodynamically favourable. Alongside BET analysis, NPA (natural population analysis), AIM (atoms in molecules) and APT (atomic polar tensor) charge analysis was also applied to the transferred chlorine atom.
Słowa kluczowe
BET, ELF, ammonia, hypochlorous acid, Hausdorff distance
Adres publiczny
Podobne publikacje
Computational Study of the Adsorption Energetics and Vibrational Wavenumbers of NH3 Adsorbed on the Ni(111) Surface
Kurten Theo, Biczysko Małgorzata, Rajamäki Timo, Laasonen Kari, Halonen Lauri