Qi Jiayuan, Hu Xiaoying, Zhu Huanhuan, Zheng Mei
College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116, People's Republic of China.
Phys Chem Chem Phys. 2016 Mar 21;18(11):8049-58. doi: 10.1039/c6cp00149a.
X-ray photoelectron (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra, as well as the ground-state electronic/geometrical structures of two important isomers of the elusive C72 fullerene family (C2v- and D6d-symmetry, respectively) and the corresponding chlorinated derivative C72Cl4, which are newly captured in the experiment, have been simulated at the density functional theory (DFT) level. Effective changes in the electronic structure and simulated X-ray spectra have been observed after chlorination. Both spectra show strong isomer dependence, therefore the "fingerprints" in the X-ray spectra offer a useful method for isomer identification of the above-mentioned fullerenes. The ultraviolet-visible (UV-vis) absorption spectroscopy of C72Cl4 has also been performed by means of time-dependent (TD) DFT calculations. The simulated UV-vis spectrum is in good agreement with the experimental results. The results of this work can provide valuable information for further experimental and theoretical studies on newly synthesized fullerene isomers and their derivatives by means of X-ray and UV-vis spectroscopy techniques.
通过密度泛函理论（DFT）水平模拟了X射线光电子能谱（XPS）和近边X射线吸收精细结构（NEXAFS）光谱，以及新近在实验中捕获的难以捉摸的C72富勒烯家族的两种重要异构体（分别为C2v和D6d对称性）及其相应的氯化衍生物C72Cl4的基态电子/几何结构。氯化后观察到电子结构和模拟X射线光谱的有效变化。两种光谱均显示出强烈的异构体依赖性，因此X射线光谱中的“指纹”为上述富勒烯的异构体鉴定提供了一种有用的方法。还通过含时（TD）DFT计算对C72Cl4的紫外可见（UV-vis）吸收光谱进行了研究。模拟的UV-vis光谱与实验结果吻合良好。这项工作的结果可为通过X射线和UV-vis光谱技术对新合成的富勒烯异构体及其衍生物进行进一步的实验和理论研究提供有价值的信息。
