Natural bond orbital analysis of some para-substituted N-nitrosoacetanilide biological molecules

Abstract

Theoretical study of several para-substituted N-nitrosoacetanilide biological molecules has been performed using density functional B3LYP method with 6-31G(d,p) basis set. Geometries obtained from DFT calculation were used to perform natural bond orbital analysis. The p characters of two nitrogen natural hybrid orbital (NHO) σ _N3–N2 bond orbitals increase with increasing σ _p values of the para substituent group on the benzene, which results in a lengthening of the N₃–N₂ bond. The p characters of oxygen NHO σ _O1–N2 and nitrogen NHO σ _O1–N2 bond orbitals decrease with increasing σ _p values of the para substituent group on the benzene, which results in a shortening of the N₂=O₁ bond. It is also noted that decreased occupancy of the localized σ _N3–N2 orbital in the idealized Lewis structure, or increased occupancy of $\sigma_{\rm N3-N2}^{\ast}$ of the non-Lewis orbital, and their subsequent impact on molecular stability and geometry (bond lengths) are also related with the resulting p character of the corresponding nitrogen NHO of σ _N3–N2 bond orbital.