In the present work, a detailed conformational study is performed using several computational methods, including density functional theory (DFT) (B3LYP), MP2 and G2MP2 on 2-Nitroso vinyl amine (NVA) in order to determine the stability order of conformers and the various possibilities of intramolecular hydrogen bonding (HB) formation. Four conformers exhibit HB . This feature, although not being the dominant factor in energetic terms, appears to be of foremost importance to define the geometry of the molecule. According to our theoretical results, oximimine conformers are more stable than the corresponding nitrosoamine and nitrosoimine analogues. Theoretical calculations show the following order for intramolecular HB strength in the conformers of title compound: [Formula: see text] The nature of intramolecular HB has been investigated by means of the Bader theory of atoms in molecules (AIM) and natural bond orbital (NBO) analysis. Also, Harmonic Oscillator Model of Aromaticity (HOMA) index as a geometrical indicator of a local aromaticity are investigated. The influence of the solvent on the stability order of conformers and the strength of intramolecular HB is considered using the Onsager reaction field model. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies confirm that charge transfer occur within the molecule. Further verification of the obtained transition state structures were implemented via intrinsic reaction coordinate (IRC) analysis. Calculations of the 1 H NMR chemical shift at GIAO/B3LYP/6–311++G** levels of theory are also presented. The excited-state properties of intramolecular HB in H -bonded systems have been investigated theoretically using the time-dependent density functional theory (TD-DFT) method. The complete vibrational assignment for three H -bonded conformers has been made on the basis of the calculated potential energy distribution (PED).
