Studies on nitramide and its methyl derivatives with ab initio calculations. IV. The harmonic force field and vibrational spectra of dimethylnitramine and its isotopic derivatives

Abstract

AbstarctThe complete harmonic vibrational force &Id of dimethylnitramine has been calculated at the Hartree-Fock level using 4-21G basis set. The harmonic force field was then scaled with scale factors previously derived from N-methylnitramine, and the vibrational spectrum of dimethylnitramine was computed. This apriori prediction, made with no reference to observations on dimethylnitramine, agrees with the experimental IR spectrum in gas phase with a mean deviation of 8.4 cm-1. Some of the scale factors were reoptimized by fitting of the computed force field to experimental data. The new set of scale factors reduced the mean deviation to 4.5 cm-l, and was used to predict the vibrational spectrum of deuterated form of dimethylnitraminc(-6D). Dipole moment derivatives were also calculated and used to predict infrared intensities which are comparable with experimental values.