Catalytic effect of water, water dimer, HCOOH and H₂SO₄ on the isomerisation of HON(O)NNO₂ to ON(OH)NNO₂: a mechanism study

Abstract

Electronic supplementary information (ESI) available: Geometrical parameters for the reaction of HN(NO2)2 to O2NNN(O)OH without and with catalyst X (X = H2O, (H2O)2, HCOOH and H2SO4,) optimized at the CBS-QB3 level of theory respectively describes in Figure S1 and Figure S2, respectively. Wiberg bond indices (WBI) and Atom-atom overlap-weighted NAO bond order (ANBO) for X-Y bond of the TSn (n = 3-6) in the isomerization of HON(O)NNO2 to ON(OH)NNO2 with HCOOH, H2SO4, HN(NO2)2 and HON(O)NNO2) calculated for the model compounds at the CBS-QB3 level describes in Table S1.

Decomposition Pathways of Ammonium Dinitramide (ADN) and its HNO3‐Clusters Elucidated by DFT‐Calculations

“…Our result agrees with a previous study by Zhang et al. [28] performed at the CBS‐QB3 level (barrier of 141.4 kJ/mol). Coordination of HNO 3 to HDN (resulting in [NO 3 H_HDN]) lowers this barrier to 45 kJ/mol in vacuo since the nitric acid mediates the proton transfer by accepting and donating the proton from and to the HDN moiety (Figure 2, results in solution are very similar).…”

“…The molecular structures of the HDN isomers and the corresponding isomerization barriers have been studied before [28, 29] and we can confirm their findings (cf. supplement for more details).…”

“…Zhang et al. [28] observed analogous catalytic effects with other acids such as H 2 SO 4 and water molecules.…”

“…Thus, fundamental understanding of the mechanisms of ADN decomposition has become a research topic of high interest initiating a multitude of experimental [11–19] and theoretical studies [20–28]. In a recent theoretical study by Izato et al.…”

OH• + HCl Reaction at the Surface of a Water Droplet: An Ab Initio Molecular Dynamical Study

“…In the atmosphere, water can exist in various forms, like cloud droplets, liquid aerosols, water clusters, and so forth. − Naturally, one cannot imagine the atmospheric chemistry without considering the role of water in the atmospheric chemical reactions. Consequently, several experimental as well as theoretical research groups have put lots of effort into investigating the effect of water on the atmospherically important chemical reactions. − In most of these studies, the water has been treated as a gaseous molecule, that is, monomer, dimer, trimer, and so forth. − ,, Only recently, some of the works have considered the surface of a water droplet as a platform to ensue a chemical reaction. ,,− Although it is known since long that the water droplets may play a crucial role in atmospheric chemistry, slow progress in experimental and theoretical work can be attributed to the lack of appropriate tools. Although the advent of some modern spectroscopic tools, like second-harmonic generation, X-ray photoelectron spectroscopy, and so forth, helps in circumventing the technical bottleneck of experimental studies, it is still challenging to study the high reactive systems on the air–water interface experimentally.…”