First-principles computational studies of the torsional potential energy surface of the sec-butyl radical

Abstract

First-principles calculations were carried out to investigate the torsional potential energy surface (PES) of the sec-butyl radical. All the wave function methods employed predict a cis-like stable conformation with a dihedral angle of about 47° in addition to the trans-like global minimum conformation and a gauche conformation. However, most of the popular density functional approaches predict only the latter two local minima and lack the cis conformation that was experimentally observed. On the other hand, some density functional methods that incorporate the exact exchange and asymptotically corrected correlation functionals can locate the cis conformation successfully. The basis-set effect was also measured using popular B3LYP and MP2 Hamiltonians: only moderate shape changes were found for PES profiles upon basis-set variations. The stationary structures and their Hessians were obtained at both MP2 and B3LYP levels, with or without incorporating the zero-point energies. Opposite to the relative stability within the Born–Oppenheimer approximation, the cis conformation is more stable than the gauche conformation upon the zero-point correction, consistent with the experiment observations.