A quantum-chemical study of the structure and conformational dynamics of the acrolein molecule in the ground electronic state

Abstract

The geometric parameters (including vibrationally averaged parameters), energy differences (ΔE) between the s-cis and s-trans conformers, and barrier to internal rotation (Vt) were calculated for the acrolein molecule CH2=CHCHO by various quantum-chemical methods (MP2, DFT, CASSCF, QCISD, CCSD(T), and MR-AQCC). The MP2 and B3LYP methods were used to calculate internal rotation potential functions and vibrational frequencies; the calculations were performed in various anharmonic approximations. To refine the ΔE and Vt values, two-dimensional (using a basis set of atomic orbitals) VFPA extrapolation procedure was applied, which allowed the results to be estimated in the FCI/CBS approximation taking into account nonadiabaticity, core correlation effects, and changes in the difference between zero point energies.