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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Acknowledgements

We gratefully thank the National Natural Science Foundation of China (Grant No. 10774039) and the grant from Development Program in Science and Technology of Henan Province (Grant No. 102300410114), Foundation for University Key Teacher by the Ministry of Education of Henan Province, and Henan University of Science and Technology for Young Scholars (Grant No. 2009QN0032) for their support of this work.

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