Amelines-Sarria Oscar, Basiuk Vladimir A, Duarte-Alaniz Víctor, Rivera Margarita
Instituto de Física, Universidad Nacional Autónoma de México, Sendero Bicipuma, Cd. Universitaria, C.P. 04510, Del. Coyoacán, Ciudad de México, Mexico.
Phys Chem Chem Phys. 2015 Nov 7;17(41):27399-408. doi: 10.1039/c5cp03921e.
The noncovalent dyad of tetraphenylporphine and C60 fullerene (H2TPP···C60) and the tetraphenylporphine dimer (H2TPP···H2TPP) were studied by density functional theory (DFT), using functionals that incorporate empirical dispersion correction (DFT-D), functionals that use a long-range correction (LC) scheme, a hybrid functional (B3LYP) and a highly parametrized empirical exchange-correlation functional (M05-2X). The results were compared to X-ray structures and interaction energies reported in previous experimental and theoretical studies. It was found that B3LYP and CAM-B3LYP functionals fail to reproduce the X-ray structures and binding energies of the TPP···C60 system. DFT-D functionals overestimated the π···π energy interactions for both systems, however, the optimized structures agree well with those observed experimentally. The LC-BLYP functional predicts geometries similar to X-ray structures; nevertheless, due to the lack of correction in the dispersion energy, the predicted energies for both model systems are low. On the other hand, the M05-2X functional exhibited the best performance. Both the structures and binding energies calculated with M05-2X are consistent with experimental and theoretical evidence reported by other authors, as well as with our experimental results obtained by means of atomic force microscopy on H2TPP thin films grown on the HOPG/C60 substrate by physical vapor deposition.
采用包含经验色散校正的泛函（DFT-D）、使用长程校正（LC）方案的泛函、杂化泛函（B3LYP）以及高度参数化的经验交换相关泛函（M05-2X），通过密度泛函理论（DFT）对四苯基卟啉与C60富勒烯的非共价二元体系（H2TPP···C60）以及四苯基卟啉二聚体（H2TPP···H2TPP）进行了研究。将结果与先前实验和理论研究中报道的X射线结构及相互作用能进行了比较。发现B3LYP和CAM-B3LYP泛函无法重现TPP···C60体系的X射线结构和结合能。DFT-D泛函高估了两个体系的π···π能量相互作用，不过，优化后的结构与实验观测结果吻合良好。LC-BLYP泛函预测的几何结构与X射线结构相似；然而，由于在色散能方面缺乏校正，该泛函预测的两个模型体系的能量都偏低。另一方面，M05-2X泛函表现出最佳性能。用M05-2X计算得到的结构和结合能与其他作者报道的实验和理论证据一致，也与我们通过原子力显微镜对通过物理气相沉积在HOPG/C60衬底上生长的H2TPP薄膜所获得的实验结果一致。
