Nitrosyl Hypofluorite: Local Density Functional Study of a Problem Case for Theoretical Methods. (Reannouncement with New Availability Information).

摘要

Local density functional (LDF) theory can successfully reproduce the previously published vibrational spectra and the salient geometrical parameters derived from them for FONO for which conventional ab initio methods (CISD/6-31G*) fail. LDF theory was used to calculate the geometries, vibrational spectra, force fields, and charge distributions for the three isomers cis-FONO, trans-FONO, and FNO2. It's shown that FNO2 is 40.8 kcal mol-1 more stable than cis-FONO, which in turn is favored by 25.2 kcal mol-1 over the trans isomer. It is shown that the previously published approximate mode descriptions for FONO are correct but that the observed spectra must be due to cis-FONO and not to the trans isomer as previously proposed. The bonding in cis-FONO is best rationalized in terms of an F atom loosely bonded through an oxygen atom to an NO, molecule, resulting in the following structural parameters: gamma (sub F-O)= 1.673 angstrom, gamma (sub FO-N)= 1.216 angstrom, gamma (sub N-O)= 1.190 angstrom, angle FON = 118.0 deg, and angle ONO = 135.2 deg.