Transient absorption anisotropy study of ultrafast energy transfer in porphyrin monomer, its direct meso-meso coupled dimer and trimer

被引:49
作者
Min, CK
Joo, T
Yoon, MC
Kim, CM
Hwang, YN
Kim, D
Aratani, N
Yoshida, N
Osuka, A [1 ]
机构
[1] Pohang Univ Sci & Technol, Dept Chem, Div Mol & Life Sci, Pohang 790784, South Korea
[2] Yonsei Univ, Natl Creat Res Initiat Ctr Ultrafast Opt Characte, Seoul 120749, South Korea
[3] Yonsei Univ, Dept Chem, Seoul 120749, South Korea
[4] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan
关键词
D O I
10.1063/1.1357438
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Transient absorption anisotropies of the Zn(II)porphyrin monomer, its direct meso-meso coupled dimer, and trimer are measured in the B (Soret) band region by sub-30 fs laser pulses. It is shown that detailed information on the electronic structures and energy transfer dynamics can be obtained from the anisotropy and the magic angle data. The anisotropies of all three molecules exhibit remarkable behaviors in the first 200 fs region. Experimental observations can be accounted for adequately by treating the transient absorption signal as an explicit sum of ground state bleach and excited state stimulated emission contributions. In the monomer, the anisotropy decay denotes an oscillatory feature followed by a 100 fs time constant exponential decay. It is argued that the B-x and B-y transitions of the porphyrin monomer are nondegenerate with an energy splitting of similar to 170 cm(-1). Furthermore, equilibration of the excitation energy within the B states is slightly underdamped. Excitation of the monomerlike B band of the dimer (trimer) leads to ultrafast similar to 30 fs (60 fs) anisotropy decay and a subsequent rise with similar to 60 fs (70 fs) time constant. It is concluded that the anisotropy decay is due to the ultrafast energy transfer to the low-energy exciton split B band, while the rise is due to the redshift of the excited state stimulated emission spectrum thereby decreasing the contribution of the excited state stimulated emission component in the overall transient absorption signal. (C) 2001 American Institute of Physics.
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页码:6750 / 6758
页数:9
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