Abstract
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 C2NNO 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 (C2H5)2N-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.
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Notes
Number ‘3’ is used as a continuation of the previous nitrosamines H2NNO (1) and (CH3)2NNO (2), see ref. [25]
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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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do Monte, S.A., de Andrade, R.B., Ventura, E. et al. Ab initio and DFT conformational study on N-nitrosodiethylamine, (C2H5)2N-N=O. J Mol Model 18, 339–350 (2012). https://doi.org/10.1007/s00894-011-1079-3
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DOI: https://doi.org/10.1007/s00894-011-1079-3