jp508392j_si_001.pdf (51.94 kB)
0/0

Generalized Valence Bond Description of Chalcogen–Nitrogen Compounds. II. NO, F(NO), and H(NO)

Download (51.94 kB)
journal contribution
posted on 05.03.2015 by Tyler Y. Takeshita, Thom H. Dunning
The electronic structure of the ground state of NO and those of F­(NO) and H­(NO), that is, the XNO and NOX isomers with X = F, H, were analyzed within the framework of generalized valence bond theory. In distinct contrast to the ground state of NS, it was found that the two-center, three-electron π interaction in NO­(X2Π) is composed of a lone pair on O and a singly occupied orbital on N. Thus, F and H addition to NO preferentially leads to FNO and HNO. Somewhat surprisingly, the NOF and NOH isomers were found to be weakly bound, although for different reasons. The NOF state has a very unusual through-pair interaction with a NO–F bond length 0.444 Å longer than its covalent counterpart in OF­(X2Π), while NOH arises from the N­(2D) + OH­(X2Π) separated atom limit, similar to what we found for NSH.

History

Exports