Internal rotation potential functions of the acryloyl chloride molecule in the ground (S0) and excited (S1) electronic states

The internal rotation potential function of the acryloyl chloride molecule in the S0 and S1 electronic states was reproduced using systems of torsional vibration levels obtained for its trans and cis isomers by analyzing the vibrational structure of the UV spectrum of the molecule. The kinematic factor F in the S0 ground state was calculated including geometric parameter relaxation as a function of internal rotation angle. The torsional potential parameters in the S0 state obtained in this work were substantially different from those determined from the infrared Fourier-transform spectrum ignoring the resonance perturbation of the level with v = 3. The form of the internal rotation potential function and the higher stability of the trans isomer (the main isomer) were substantiated by high-level quantum-mechanical calculations.