Consistent assignment of the vibrations of monosubstituted benzenes

We investigate the consistency of the labeling and assignments of the vibrations of the monosubstituted benzenes in the electronic ground state. In doing so, we also identify some inconsistencies in the labeling of the benzene modes. We commence by investigating the behavior of the benzene vibrations as one hydrogen is replaced by an artificial atomic substituent of increasing mass via quantum chemical calculations; the wavenumber variations with mass give insight into the assignments. We also examine how well the monohalobenzene vibrations can be described in terms of the benzene ones: consistent with some recent studies, we conclude that this is futile in a significant number of cases. We then show that isotopic wavenumbers obtained by artificially changing the mass of the fluorine atom in fluorobenzene are in very good agreement with the wavenumbers obtained via explicit calculation for the relevant monohalobenzene (chlorobenzene, bromobenzene, and iodobenzene) vibrations. As a consequence, we propose that the vibrations of monofluorobenzene be used as the basis for labelling the vibrational assignments of monosubstituted benzenes. As well as the four monohalobenzenes, we also apply this approach to the vibrations of aniline, toluene, benzonitrile, phenylacetylene, phenylphosphine, and nitrobenzene. This has allowed a much more consistent picture of the vibrational assignments to be obtained across ten monosubstituted benzenes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3638266]