One- and Two-Dimensional Torsion-Inversion Models for the Fluoral Molecule (CF3CHO) in Excited Electronic States

Abstract

The structure of the conformationally nonrigid fluoral molecule (CF3CHO) in the ground (S0) and lowest excited triplet (T1) and singlet (S1) electronic states was studied by ab initio quantum-chemical methods. The equilibrium geometric parameters and harmonic vibrational frequencies of the molecule in these electronic states were determined. The calculations demonstrated that the electronic excitation causes substantial changes in the molecular structure involving the rotation of the CF3 top and the deviation of the CCHO carbonyl fragment from planarity. The quantum-mechanical problems for large-amplitude vibrations, namely, for the torsional vibration in the S0 state and the torsional and inversion vibrations (nonplanar carbonyl fragment) in the T1 and S1 states, were solved in the one- and two-dimensional approximations. A comparison of the results of calculations revealed the correlation between the torsional and inversion motions.