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Quantum chemical topology: the electronic structure of the alkaline nitrites MONO (M = Li, Na, K) studied by means of topological analysis of the electron localization function.
Autorzy
Rok wydania
2010
Czasopismo
International Journal of Quantum Chemistry
Numer woluminu
110
Strony
1890-1900
DOI
10.1002/qua.22383
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
In the search of the protocovalent bonding, previously recognized in the nitrous acid (HONO), a nature of the chemical bonds in the alkaline nitrites MONO (M = Li, Na, K) has been studied by means of the topological analysis of the Electron Localization Function (ELF) and Electron Localizability Indicator (ELI‐D). Calculations carried out with the B3LYP and MP2(full) methods, in conjunction with the aug‐cc‐pVTZ and 6‐311++G(3df,3pd) basis sets, revealed the cis (C2v, more stable) and trans (Cs) isomers as minima on PES. Alkaline nitrites consist of the alkali metal cation Mδ+ interacting, mainly via electrostatic forces, with the nitrite anion [ONO]δ− (δ ≈ 1e). The covalent NO bonds are characterized by disynaptic basins V(N,O) with the basin populations: 1.58÷1.62e for cis‐Mδ+[ONO]δ− but 1.39÷1.49e for single NO bond and 1.81÷1.87e for formally double NO bond in trans Mδ+[ONO]δ−. The protocovalent nitrogen–oxygen bond has not been observed. The NO bonds are slightly polarized towards the nitrogen atom with the polarity index pNO ≤ 0.12. Two different sets of the hybrid (Lewis) structures are compared leading to different pictures of the bonding. According to NBO data there is a delocalization between the single NO and double NO type bonds, meanwhile results of the ELF analysis emphasize an electron delocalization between the single NO and ionic O−N+ hybrids. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010
Słowa kluczowe
electron localization function, chemical bond, B3LYP, MP2, DFT
Adres publiczny
https://doi.org/10.1002/qua.22383
Strona internetowa wydawcy
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