HD isotope effect of methyl internal rotation for acetaldehyde in ground state as calculated from a multicomponent...

We have analyzed the differences in the methyl internal rotation induced by the HD isotope effect for acetaldehyde (CH(3)CHO) and deuterated acetaldehyde (CD(3)CDO) in ground state by means of the multicomponent molecular orbital (MC_MO) method, which directly accounts for the quantum effects of protons and deuterons. The rotational constant of CH(3)CHO was in reasonable agreement with experimental one due to the adequate treatment of the protonic quantum effect by the MC_MO method. The C-D bond distances were about 0.007 A shorter than the C-H distances because of the effect of anharmonicity of the potential. The Mulliken population for CD(3) in CD(3)CDO is larger than that for CH(3) in CH(3)CHO because the distribution of wavefunctions for the deuterons was more localized than that for the protons. The barrier height obtained by the MC_MO method for CH(3)CHO was estimated as 401.4 cm(-1), which was in excellent agreement with the experimentally determined barrier height. We predicted the barrier height of CD(3)CDO as 392.5 cm(-1). We suggest that the internal rotation of the CD(3) group was more facile than that of the CH(3) group because the C-D bond distance was observed to be shorter than the C-H distance. Additionally the localized electrons surrounding the CD(3) group in CD(3)CDO caused the extent of hyperconjugation between the CD(3) and CDO groups to be smaller than that in the case of CH(3)CHO, which may have also contributed to the observed differences in methyl internal rotation. The differences in bond distances and electronic populations induced by the H/D isotope effect were controlled by the difference in the distribution of wavefunctions between the protons and deuterons.