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Substituent effect on structure, electron density, and intramolecular hydrogen bonding in nitroso‐oxime methane
Author(s) -
Yoosefian Mehdi,
Raissi Heidar,
Nadim Emad Saleh,
Farzad Farzaneh,
Fazli Mustapha,
Karimzade Elham,
Nowroozi Alireza
Publication year - 2010
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.22793
Subject(s) - intramolecular force , chemistry , natural bond orbital , aromaticity , density functional theory , computational chemistry , atoms in molecules , hydrogen bond , substituent , ab initio , molecule , stereochemistry , organic chemistry
Density functional calculations with Beck's three‐parameter hybrid method using the correlation functional of Lee, Yang, and Parr (B3LYP) were carried out for investigation of the intramolecular hydrogen bond strength in Nitroso‐oxime methane and its derivatives. Also, vibrational frequencies for them were calculated at the same level of theory. The π‐electron delocalization parameter ( Q ) and as a geometrical indicator of a local aromaticity, the geometry‐based harmonic oscillator measure of aromaticity index has been applied. Additionally, the linear correlation coefficients between substituent constants and selected parameters in R position have calculated. The obtained results show that the hydrogen bond strength is mainly governed by the resonance variations inside the chelate ring induced by the substituent groups. The topological properties of the electron density distributions for OH ··· O intramolecular bridges have been analyzed in terms of the Bader theory of atoms in molecules (AIM). Correlations between the H‐bond strength and topological parameters have been also studied. The electron density (ρ) and Laplacian (∇ 2 ρ) properties, estimated by AIM calculations, show that O ··· H bond have low ρ and negative (∇ 2 ρ) values (consistent with covalent character of the HBs), whereas OH bond have positive (∇ 2 ρ) Furthermore, the analysis of hydrogen bond in this molecule and its derivatives by quantum theory of natural bond orbital (NBO) methods fairly support the ab initio results. Natural population analysis data, the electron density, and Laplacian properties as well as υ(OH) and γ(OH) were further used for estimation of the hydrogen bonding interactions and the forces driving their formation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011