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

作者：Takeshita Tyler Y; Dunning Thom H Jr^*

来源：Journal of Physical Chemistry A, 2015, 119(9): 1456-1463.

DOI：10.1021/jp508392j

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 pi interaction in NO(X-2 Pi) 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 NO-F 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 angstrom longer than its covalent counterpart in OF(X-2 Pi), while NOH arises from the N(D-2) + OH(X-2 Pi) separated atom limit, similar to what we found for NSH.

• 出版日期2015-3-5