Photoinduced Charge Transfer Processes of Zinc Porphyrin Derivatives for Dye-sensitized Solar Cells  

作　　者：ZHAO Yi-dan FU Jing-jing LI Hai-bin DONG Hao LIAO Yi 

机构地区：[1]Department of Chemistry, Capital Normal University, Beijing 100048, P. R. China [2]Institute of Chemistry for Functionalized Material, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China

出　　处：《Chemical Research in Chinese Universities》2013年第5期974-981,共8页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（No.11179033）, the Program for New Century Excellent Talents in University of China（No.NCET- 10-0011）, the Beij ing Natural Science Foundation, China（N o.2132017 ） and Program for the Top Young Talents of Higher Learning Institutions of B eijing Municipality China.

摘　　要：We studied the excitation energies of zinc porphyrin（ZnP） and zinc porphyrin analogues（ZnP-R） with long-range corrected（LC） density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was lbund that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G（d） basis set. Excited-state geometry optimiza- tions lbr all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc（F）12] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis（4-hexylphenyl）amino] partially. The computed excited-state radiative lifetime（r） for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur alter vibrational relaxation of excited state.We studied the excitation energies of zinc porphyrin（ZnP） and zinc porphyrin analogues（ZnP-R） with long-range corrected（LC） density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was lbund that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G（d） basis set. Excited-state geometry optimiza- tions lbr all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc（F）12] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis（4-hexylphenyl）amino] partially. The computed excited-state radiative lifetime（r） for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur alter vibrational relaxation of excited state.

关 键 词：Excitation energy Long-range corrected（LC） functional Zinc porphyrin Zinc porphyrin analogue Elec-tron injection 

分 类 号：O627.23[理学—有机化学] TM914.4[理学—化学]