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 no1 →σ*O3-N2 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 σo3-N2 orbital in the idealized Lewis structure,or increased occupancy of σo3-N2 of the non-Lewis orbital, and their subsequent impact on molecular stability and geometry (bond lengths) are related with the resulting p character of the corresponding sulfur natural hybrid orbital (NHO) of σo3-N2 bond orbital. In addition, the charge transfer energy decreases with the increase of the Hammett constants of subsitutent groups.
基金项目
We gratefully thank the National Natural Science Foundation of China(10774039)
grant from Development Program in Science and Technology of Henan Province(102300410114)
Foundation for University Key Teacher by the Ministry of Education of Henan Province()
Henan University of Science and Technology for Young Scholars(2009QN0032)
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