Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA.
J Phys Chem A. 2009 Feb 26;113(8):1601-7. doi: 10.1021/jp8095709. Epub 2009 Feb 5.
High level ab initio calculations, utilizing coupled cluster theory with quasi-perturbative triple excitations and augmented quadruple zeta level basis sets, have been used to determine the structures and relative energies of the four stationary points on the 1,3-butadiene torsional potential curve. Corrections were applied in order to minimize the residual basis set error, as well as account for core/valence correlation and scalar relativistic effects. Higher order correlation recovery was also included to improve our estimate of the relative energies. The transition state separating the trans and gauche rotamers lies 26.8 kJ/mol above the trans global minimum. The gauche rotamer lies 12.6 kJ/mol above the trans rotamer and the s-cis form is a transition state 2.0 kJ/mol higher than the gauche rotamer (excluding zero point energies).
采用耦合簇理论与准微扰三激发和扩充四重zeta 基组相结合的高水平从头计算，确定了 1,3-丁二烯扭转势能曲线上四个稳定点的结构和相对能量。为了最小化剩余基组误差，以及考虑核/价相关和标量相对论效应，进行了修正。还包括高阶相关恢复，以提高我们对相对能量的估计。将反式和顺式构象分开的过渡态位于反式全局最低点以上 26.8 kJ/mol。 gauche 构象比反式构象高 12.6 kJ/mol，s-顺式构象比 gauche 构象高 2.0 kJ/mol，而不是 gauche 构象（不包括零点能）。
