Theoretical investigation of some O-nitrosyl carboxylate biologic molecules — A natural bond orbital study

Abstract

Theoretical study of several O-nitrosyl carboxylate compounds have been performed using quantum computational ab initio RHF and density functional B3LYP and B3PW91 methods with 6-31G** basis set. Geometries obtained from DFT calculations were used to perform the natural bond orbital (NBO) analysis. It is noted that weakness in the O₃-N₂ bond is due to n_{{\mathrm{O}}_{\mathrm{1}}}\to {\sigma }_{{\mathrm{O}}_{\mathrm{3}}-{\mathrm{N}}_{\mathrm{2}}}^{*} delocalization and is responsible for the longer O₃-N₂ bond lengths in O-nitrosyl carboxylate compounds. It is also noted that decreased occupancy of the localized {\sigma }_{{\mathrm{O}}_{\mathrm{3}}-{\mathrm{N}}_{\mathrm{2}}} orbital in the idealized Lewis structure, or increased occupancy of {\sigma }_{{\mathrm{O}}_{\mathrm{3}}-{\mathrm{N}}_{\mathrm{2}}}^{*} of the non-Lewis orbital, and their subsequent impact on molecular stability and geometry (bond lengths) are related with the resulting BoldItalic character of the corresponding sulfur natural hybrid orbital (NHO) of {\sigma }_{{\mathrm{O}}_{\mathrm{3}}-{\mathrm{N}}_{\mathrm{2}}} bond orbital. In addition, the charge transfer energy decreases with the increase of the Hammett constants of subsitutent groups.

Keywords

natural bond orbital (NBO) / O-nitrosyl carboxylate compounds / second order delocalization energies / natural hybrid

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