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Ab initio and DFT conformational study on nitrosamine (H2N–N=O) and N-Nitrosodimethylamine [(CH3)2N–N=O]

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Abstract

Ab initio and DFT calculations have been performed to characterize some ground state structures of the title molecules. Relative energies, rotational barriers, NBO charges, and dipole moments (µ) have been calculated and analyzed. It has been confirmed that only highly correlated methods (e.g., CCSD) are able to yield the non-planar structure as a minimum, for the H2NNO molecule. On the other hand, all computational levels here employed are able to yield a planar C2NNO frame for the (CH3)2NNO as a minimum. Important correlations between atomic charges and bond distances are discussed. Replacement of H by methyl group increases the rotational barrier and µ values by at least 3 kcal/mol and 0.4 D, respectively. The largest µ values are obtained for the structures in which the nitrogen lone pair is parallel to the NO group π system, and are consistent with a larger contribution of a dipolar resonance structure.

Graphical abstract

The dipole moments, NBO charges, geometries, and relative energies of these structures have been compared, at B3LYP, MP2, and CCSD levels.

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Acknowledgments

The authors would like to thank Professor Júlio S. Rebouças for his valuables suggestions. We are also grateful to the CNPq (476201/2009-8, 303856/2008-4, 303860/2008-1, 570565/2008-1) and CAPES (Brazilian agencies) for financial support.

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Authors and Affiliations

  1. Departamento de Química, CCEN, Universidade Federal da Paraíba, João Pessoa, PB, 58059-900, Brazil

    Silmar A. do Monte, Elizete Ventura, Tamires F. da Costa & Sidney R. de Santana

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  1. Silmar A. do Monte
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  2. Elizete Ventura
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  3. Tamires F. da Costa
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  4. Sidney R. de Santana
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Correspondence to Silmar A. do Monte.

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do Monte, S.A., Ventura, E., da Costa, T.F. et al. Ab initio and DFT conformational study on nitrosamine (H2N–N=O) and N-Nitrosodimethylamine [(CH3)2N–N=O]. Struct Chem 22, 497–507 (2011). https://doi.org/10.1007/s11224-010-9721-8

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  • DOI: https://doi.org/10.1007/s11224-010-9721-8

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