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Ab initio and DFT conformational study on N-nitrosodiethylamine, (C2H5)2N-N=O.
do Monte, Silmar A; de Andrade, Railton B; Ventura, Elizete; de Santana, Sidney R.
Afiliação
  • do Monte SA; Departamento de Química, CCEN, Universidade Federal da Paraíba, João Pessoa, Brazil. silmar@quimica.ufpb.br
J Mol Model ; 18(1): 339-50, 2012 Jan.
Article em En | MEDLINE | ID: mdl-21523530
Ab initio (MP2) and DFT (B3LYP) calculations, using the cc-pVTZ and aug-cc-pVTZ basis sets, have been performed to characterize some stationary points on the ground state potential energy surface of the title molecules. Several properties as, for instance, relative energies, the barriers for NO rotation around the NN bond, NBO charges on O and amino N atoms, as well as the dipole moments, have been calculated and analyzed in the light of the structures found. Both computational levels here employed yield three minima, in which the C(2)NNO frame is 'planar' or 'quasi-planar'. Important correlations between NBO charges and geometric parameters, as well as between some structural features and dipole moments are also discussed. A total of 17 structures have been found for the (C(2)H(5))(2)N-N=O molecule. Two ranges of values have been obtained for the dipole moment, with the largest values occurring for the structures in which the nitrogen lone pair is parallel to the NO group π system. For instance, these two ranges are from ~4.1 to 4.5 D, and from ~1.6 to 2.1 D, at the MP2/cc-pVTZ level. These ranges are consistent with a larger and a smaller contribution of a dipolar resonance structure, respectively. As the method or basis set changes the values of the dipole moments change by at most ~0.23 D.
Assuntos

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Dietilnitrosamina / Modelos Químicos Idioma: En Revista: J Mol Model Assunto da revista: BIOLOGIA MOLECULAR Ano de publicação: 2012 Tipo de documento: Article País de afiliação: Brasil País de publicação: Alemanha

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Dietilnitrosamina / Modelos Químicos Idioma: En Revista: J Mol Model Assunto da revista: BIOLOGIA MOLECULAR Ano de publicação: 2012 Tipo de documento: Article País de afiliação: Brasil País de publicação: Alemanha