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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
Author(s) -
Berski Sławomir,
Latajka Zdzisław
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22383
Subject(s) - electron localization function , chemistry , delocalized electron , natural bond orbital , ionic bonding , covalent bond , chemical bond , alkali metal , crystallography , topology (electrical circuits) , ion , computational chemistry , electron , density functional theory , physics , organic chemistry , mathematics , quantum mechanics , combinatorics
Abstract 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 ( C 2v , more stable) and trans (C s ) isomers as minima on PES. Alkaline nitrites consist of the alkali metal cation M δ+ 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 ‐M δ+ [ONO] δ− but 1.39÷1.49e for single NO bond and 1.81÷1.87e for formally double NO bond in trans M δ+ [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 p NO ≤ 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