FONO - A difficult case for theory and experiment

Abstract

High levels of ab initio theory are used to investigate the equilibrium structures, vibrational spectra, and relative energetics of FNO2, cis-FONO, and trans-FONO isomers. FNO2 is determined to be 36.9 +/- 2.5 kcal/mol (0 K) more stable than cis-FONO, which is more stable than trans-FONO by 2.5 +/- 1.0 kcal/mol (0 K). The molecular structure of cis-FONO is shown to have typical F-O and central O-N single bond distances, indicating that cis-FONO has a structure analogous to HONO. The computed vibrational spectrum of cis-FONO is shown to be consistent with IR matrix isolation experiments, including isotopic shifts. The experimentally deduced structure of FONO is shown to be incorrect because one of the vibrational bands included in the normal coordinate analysis is either a combination band or an overtone.