Bohl E, Mignolet B, Johansson J O, Remacle F, Campbell E E B
EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
Phys Chem Chem Phys. 2017 Sep 13;19(35):24090-24099. doi: 10.1039/c7cp03913a.
TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.
本文介绍了一系列多环烃和环烷烃的低能里德堡态的含时密度泛函理论（TD-DFT）计算。随着分子复杂度的增加，预测了s、p和d里德堡系列首个成员的结合能和光电子角分布的系统变化。计算得到的结合能与可用于比较的文献值非常吻合。给出了并五苯的实验角分辨光电子能谱结果，再次表明其与结合能的理论预测以及光电子角分布都非常吻合。小“空心”碳结构立方烷、金刚烷和十二面体烷的戴森轨道与原子s、p和d轨道有密切相似性，类似于富勒烯报道的超原子分子轨道（SAMO），这表明这些低能、弥散态并不局限于π共轭分子。
