An analysis of the vibrational structure of high-resolution UV spectra and long-wave IR Fourier transform spectra in studies of internal rotation in molecules

Abstract

The methods for analyzing the vibrational structure of high-resolution UV spectra and long-wave IR Fourier transform spectra in studies of internal rotation in α,β-unsaturated carbonyl compounds R4R3C=CR2-COR1 (R1 = F, Cl; R2 = R3 = R4 = H, CH3) are compared. These methods were found to give different experimental values for systems of torsional vibration energy levels up to high quantum numbers, torsional frequencies (0–1 transitions), and anharmonicity coefficients x 11 for trans and cis isomers of the same molecules in the ground electronic state (S 0). It was shown that the experimental technique for analyzing the vibrational structure of UV spectra excludes the hydrolysis of compounds under study. Taking into account Fermi resonance and numerous Deslandres tables constructed for trans and cis isomers provides reliable determination of values necessary for the construction of internal rotation potential functions, because they are multiply repeated in various Deslandres tables. An analysis of the vibrational structure of UV spectra gives more reliable V n internal rotation potential function parameters. The V n parameter values were substantiated by quantum-mechanical calculations performed by other authors.