Investigating the Resonance in Nitric Acid and the Nitrate Anion Based on a Modern Bonding Analysis*
Malte Fugel A , Florian Kleemiss A , Lorraine A. Malaspina A , Rumpa Pal A , Peter R. Spackman B , Dylan Jayatilaka B and Simon Grabowsky A C
+ Author Affiliations
- Author Affiliations
A University of Bremen, Department 2 – Biology/Chemistry, Institute of Inorganic Chemistry and Crystallography, Leobener Str. 3, 28359 Bremen, Germany.
B University of Western Australia, School of Molecular Sciences, 35 Stirling Highway, Perth, WA 6009, Australia.
C Corresponding author. Email: simon.grabowsky@uni-bremen.de
Australian Journal of Chemistry 71(4) 227-237 https://doi.org/10.1071/CH17583
Submitted: 10 November 2017 Accepted: 22 December 2017 Published: 19 February 2018
Abstract
The nitrate anion, NO3−, is often regarded as a textbook example for the very fundamental concept of resonance. Usually, three equivalent resonance structures with one N–O double bond and two N–O single bonds are considered. Consequently, each of the three N–O bonds should have a partial double bond character. In this study, we analyse the resonance in NO3− in comparison with the related species HNO3 and FNO3 by applying a combination of the Quantum Theory of Atoms in Molecules (QTAIM), a natural bond orbital (NBO) analysis, the electron localizability indicator (ELI), and valence bond (VB) calculations. Despite the fundamental importance of nitrate salts and nitric acid for the environment, chemistry, and industry, a bonding analysis is absent from the literature so far. The classical resonance structures are clearly reflected by the bond analysis tools, but are not the only contributions to the bonding situation. The resonance in HNO3 and FNO3 is greatly perturbed by the hydrogen and fluorine atoms. In addition to theoretical calculations, experimental electron density and wave function refinements were carried out on a KNO3 crystal.
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