TY - JOUR
T1 - Investigating the Resonance in Nitric Acid and the Nitrate Anion Based on a Modern Bonding Analysis
AU - Fugel, Malte
AU - Kleemiss, Florian
AU - Malaspina, Lorraine A.
AU - Pal, Rumpa
AU - Spackman, Peter R.
AU - Jayatilaka, Dylan
AU - Grabowsky, Simon
PY - 2018/1/1
Y1 - 2018/1/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85046849230&partnerID=8YFLogxK
U2 - 10.1071/CH17583
DO - 10.1071/CH17583
M3 - Article
AN - SCOPUS:85046849230
SN - 0004-9425
VL - 71
SP - 227
EP - 237
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 4
ER -