The vibrational spectra of amides—II. The force field and isotopic shifts of N, N-dimethyl formamide

Abstract

The effects of 16O → 18O substitution on the vibrational frequencies of N, N-dimethylformamide have been studied. To understand these and the effects of previously measured shift data due to 13C, 2H and 15N ab initio calculations of frequencies and intensities have been carried out at the 3-21G level. Accord between theory and experiment is generally good. A surprising result is the prediction of a weak band near 2000 cm −1 in DMF due to in-plane interaction between the methyl umbrella modes and the anti-symmetric CN stretch. This abnormally high frequency is explained as arising due to the planar trigonal C 3N entity. Previous problems in reproducing isotope shifts are shown to be due to this mode being previously assigned near 1500 cm −1. The effects of suppressing reference to one of a set of internal valence angles involved in a redundancy are explored. It is shown that the principal effect is to add the diagonal quadratic constant for that coordinate to all other quadratic terms involving pairs of the angles involved in the redundancy. This results in large, almost equal, interaction constants amongst this set. Such effects are seen in the present work. The ab initio field is shown to be compatible with ab initio fields of mono N-methyl amides extant in the literature.