Chemical Physics Letters, Vol.624, 53-58, 2015
Contrasting patterns of coupling between the CH stretches and the large-amplitude motions in the molecules, CH3NH2, CH3OH2+ and CH3CH2 center dot
In each of the title molecules, torsional and inversion tunneling occurs between six equivalent minima. The coupling between these large-amplitude motions and the CH stretch vibrations stems from the variation of the CH stretching force constants as a function of the torsional and inversion coordinates. First principles 2D maps of the variation of the CH-stretch force constants are reported. Although the torsional barriers differ by more than a factor of 20, the torsion-inversion-vibration coupling is similar for two of the species, CH3NH2 and CH3CH2 center dot, but is much weaker and qualitatively different in form for the third species, CH3OH2+. (C) 2015 Elsevier B.V. All rights reserved.