Ferchichi Olfa, Derbel Najoua, Jaidane Nejm-Eddine, Cours Thibaud, Alijah Alexander
LSAMA, Laboratoire de Spectroscopie Atomique, Moléculaire et Applications, Département de Physique, Faculté des Sciences, Université Tunis - El Manar, 1060 Tunis, Tunisia.
Phys Chem Chem Phys. 2017 Aug 16;19(32):21500-21506. doi: 10.1039/c7cp03134c.
There has been a disagreement amongst experimentalists and between experimentalists and theoreticians as to the gas-phase structure of dimethyl peroxide. We have investigated this problem with high-level CCSD(T)-F12 and MRCI procedures. There can be no doubt anymore that, at the minimum of the potential energy surface, the COOC fragment has a trans-structure. The dynamical structure of the molecule can, however, be different and be explained by the very slow torsional motion. We have analysed the dynamical structure using numerical wavefunctions of the torsional motion and a fully optimized potential curve of MP2/aug-cc-pVTZ quality. Computational and all experimental results are shown to be in complete agreement. The problem that has persisted for more than thirty years, highlighted in a recent review article by Oberhammer titled "Gas phase structures of peroxides: experiments and computational problems", has been resolved.
关于过氧化二甲基的气相结构，实验人员之间以及实验人员与理论人员之间一直存在分歧。我们使用高级CCSD(T)-F12和MRCI程序对这个问题进行了研究。毫无疑问，在势能面的最低点，COOC片段具有反式结构。然而，分子的动态结构可能不同，这可以用非常缓慢的扭转运动来解释。我们使用扭转运动的数值波函数和MP2/aug-cc-pVTZ质量的完全优化势能曲线分析了动态结构。计算结果与所有实验结果完全一致。在奥伯哈默最近一篇题为《过氧化物的气相结构：实验与计算问题》的综述文章中强调的持续了三十多年的问题已经得到解决。
