Structure and conformational dynamics of the dicyclopropyl ketone in the ground electronic state

• Published in: Journal of molecular structure. Theochem 2010-01, Vol.939 (1), p.14-21
• Main Authors: Rastoltseva, Ekaterina V., Bataev, Vadim A., Abramenkov, Alexander V., Pupyshev, Vladimir I., Godunov, Igor A.
• Format: Article
• Language: English
• Subjects: Conformational dynamics; Coupling of torsion motions; Dicyclopropyl ketone; Nonrigid molecule; Torsion transition energies; Valence focal-point analysis
• ISSN: 0166-1280; 1872-7999
• DOI: 10.1016/j.theochem.2009.09.033

Geometric parameters, harmonic and anharmonic vibrational frequencies, conformer energy differences and barriers to internal rotation were obtained for dicyclopropyl ketone (DCPK) in the ground electronic state through MP2, DFT, CCSD and CCSD(T) calculations. VFPA was used to improve the estimations of conformer energy differences and heights of barriers to internal rotation. The ab initio calculations demonstrated that there are three stable conformations of DCPK: the cis–cis, the cis–trans and the gauche–gauche. The energy of the gauche–gauche conformer is noticeably higher than the energy of the two other conformers, so this conformer was not found experimentally. To study the conformational dynamics of the DCPK molecule, one- and two-dimensional sections of the potential energy surface corresponding to the rotations of the cyclopropyl groups were calculated. These sections were used to calculate torsion transition energies and vibrational wave functions in anharmonic approach. It was found that there is a strong coupling of large-amplitude torsion motions in the area of the cis–cis and gauche–gauche conformers.