jp508392j_si_001.pdf (51.94 kB)
Generalized Valence Bond Description of Chalcogen–Nitrogen Compounds. II. NO, F(NO), and H(NO)
journal contribution
posted on 2015-03-05, 00:00 authored by Tyler
Y. Takeshita, Thom H. DunningThe 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.