Mukherjee Binayak, Mukherjee Manabendra
Department of Physics, Baba Farid Institute of Technology, Dehradun 248007, Uttarakhand, India.
Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064, India.
ACS Omega. 2017 Dec 22;2(12):9181-9190. doi: 10.1021/acsomega.7b01407. eCollection 2017 Dec 31.
In this work, the structural and electronic properties of perylene tetracarboxylic diimide (PTCDI) derivative molecules have been calculated using density functional theory simulations. Here, we have obtained the equilibrium geometry for certain PTCDI derivatives and calculated their occupied and unoccupied density of states separately for molecular orbitals lying in-plane (σ type) and orthogonal to the plane (π type) of the molecules. We have also simulated the X-ray absorption spectroscopy (XAS) spectra for these molecules separately for π- and σ-type orbitals. A comparison between the unoccupied density of states and XAS data has been made because both provide a description of the molecular orbitals above the Fermi level. We have observed the presence of shallow-lying σ orbitals in twisted molecules and have obtained an almost linear relationship between the abundance of these orbitals and the degree of molecular twist. Additionally, we have shown the possibility of an experimentally viable stereoisomerism in PTCDI-C3.
在这项工作中，使用密度泛函理论模拟计算了苝四羧酸二亚胺（PTCDI）衍生物分子的结构和电子性质。在此，我们获得了某些PTCDI衍生物的平衡几何结构，并分别计算了位于分子平面内（σ型）和与分子平面正交（π型）的分子轨道的占据态和未占据态密度。我们还分别针对π型和σ型轨道模拟了这些分子的X射线吸收光谱（XAS）。对未占据态密度和XAS数据进行了比较，因为两者都描述了费米能级以上的分子轨道。我们观察到扭曲分子中存在浅位的σ轨道，并获得了这些轨道的丰度与分子扭曲程度之间几乎呈线性的关系。此外，我们展示了PTCDI-C3中存在实验上可行的立体异构现象的可能性。
