DFT and TDDFT Study Related to Electron Transfer in Nonbonded Porphine···C60 Complexes

详细信息    查看全文

• 作者：Teemu L. J. Toivonen ; Terttu I. Hukka ; Oana Cramariuc ; Tapio T. Rantala ; Helge Lemmetyinen
• 刊名：Journal of Physical Chemistry A
• 出版年：2006
• 出版时间：November 9, 2006
• 年：2006
• 卷：110
• 期：44
• 页码：12213 - 12221
• 全文大小：296K
• 年卷期：v.110,no.44(November 9, 2006)
• ISSN：1520-5215

文摘

Spectroscopic properties of a ground state nonbonded porphine-buckminsterfullerene (H₂P···C₆₀) complexare studied in several different relative orientations of C₆₀ with respect to the porphine plane by using thedensity functional (DFT) and time-dependent density functional (TDDFT) theories. The geometries andelectronic structures of the ground states are optimized with the B3LYP and PBE functionals and a SVPbasis set. Excitation energies and oscillator strengths are obtained from the TDDFT calculations. The relativeorientation of C₆₀ is found to affect the equilibrium distance between H₂P and C₆₀ especially in the case ofthe PBE functional. The excitation energies of different H₂P···C₆₀ complexes are found to be practically thesame for the same excitations when the B3LYP functional is used but to differ notably when PBE is used incalculations. Existence of the states related to a photoinduced electron transfer within a porphyrin-fullerenedyad is also studied. All calculations predict a formation of an excited charge-transfer complex state, a locallyexcited donor (porphine) state, as well as a locally excited acceptor (fullerene) state in the investigatedH₂P···C₆₀ complexes.