Accurate torsional potentials in conjugated systems: ab initio and density functional calculations on 1,3-butadiene and monohalogenated butadienes

Abstract

Accurate calculations of the torsional potentials for rotation around the carbon–carbon single bond of all conceivable monohalogenated 1,3-butadienes C4 H 5X, (X ∈ [F, Cl, Br]), are presented. The parent compound, 1,3-butadiene, is also included as a benchmark and reference case. Large-scale ab initio calculations were performed at the second-order Møller–Plesset perturbation theory (MP2) and the coupled cluster, CCSD(T), levels. Additionally, density functional methods were applied. In all compounds considered, the anti- or s-trans-conformation is the most stable. For all three halogens, the 2-halo-1,3-butadiene is the most stable isomer, followed by the cis-1-halo-1,3-butadiene. Depending on the position and the type of halogen, the original 1,3-butadiene torsional potential is modified in a different manner. The modifications are particularly visible in the region of the syn- or s-cis and the gauche structures and in the barrier heights.