Ab initio study of the structure and conformations of 2-fluoroethanal in the ground and lowest excited electronic states

Abstract

The structure of the conformationally flexible 2-fluoroethanal molecule (CH2FCHO, FE) in the ground (S0) and lowest excited triplet (T1) and singlet (S1) electronic states was investigated by ab initio quantum-chemical methods. The FE molecule in the S0 state was found to exist as two conformers, viz., as cis (the F—C—C—O angle is 0°) and trans (the F—C—C—O angle is 180°) conformers. On going both to the T1 and S1 states, the FE molecule undergoes substantial structural changes, in particular, the CH2F top is rotated with respect to the core and the carbonyl CCHO fragment becomes nonplanar. The potential energy surfaces for the T1 and S1 states are qualitatively similar, viz., six minima in each of the excited states of FE correspond to three pairs of mirror-symmetrical conformers. Based on the potential energy surfaces calculated for the FE molecule in the T1 and S1 states, the one-dimensional problems on the torsion and inversion nuclear motions as well as the two-dimensional torsion-inversion problems were solved.