Abstract: Molecular structure and vibrational spectra of acetone, acetone-d3, and acetone-d6 were investigated by means of ab initio and density functional theory (DFT) calculations. The harmonic and anharmonic vibrational frequencies of the acetone isotopomers were calculated at the B3LYP (using the 6–311++G(3df,3pd) basis set) and B2PLYP (using the 6–31+(2d,p) and 6–311G(2df,p) basis sets) levels. The calculated frequencies and the Raman and infrared (IR) intensities were compared with the experimental results. Excellent agreement between calculated and observed vibrational wavenumbers was obtained. Additionally, a normal coordinate analysis (NCA) was also done by using the normal mode eigenvectors obtained at the B3LYP/6–311++G(3df,3pd) level. All fundamental vibrational bands were assigned to the normal modes with the aid of the potential energy distribution (PED) values obtained from normal coordinate calculations. To study the internal rotation of CH3 groups, single CH3 rotation and synchronous rotations of both CH3 groups (clockwise–clockwise and clockwise–counterclockwise) were analyzed using the MP2/6–311++G(3df,2pd) and B3LYP/6–311++G(3df,2pd) levels.

Keywords