Rotation -Torsion -Vibration Interaction in the Rotational Spectra of Isotopic Species of Ethyl Cyanide

Abstract

Abstract The measurements of the ground state rotational spectra of CH3CH2C15N and CH3CD2CN were extended to calculate the centrifugal distortion coefficients DJ , DJK and DK. The rotation-torsion-vibration interaction for these molecules including the normal species CH3CH2CN was studied in the rotational spectra of the first excited state of the methyl torsion and the CCN-in plane deformation. With respect to previous work a more detailed check of a model with five degrees of freedom comprising the overall rotation and the two lowest vibrations was possible. Potential parameters were fitted simultaneously to the splittings of the rotational transitions in the two lowest excited vibrational states of the three isotopic molecules. The coefficients V3 and V6 of the Fourier expansion of the hindering potential for the torsion and an interaction constant V'3c for the torsion and the CCN-in plane deformation were determined. Using these results it was possible to reproduce the frequencies of the torsional and CCN vibrations. With less success the torsional overtones could also be calculated.