Exciton Level Structure and Dynamics in Tubular Porphyrin Aggregates

详细信息    查看全文

• 作者：Yan Wan ; Anna Stradomska ; Sarah Fong ; Zhi Guo ; Richard D. Schaller ; Gary P. Wiederrecht ; Jasper Knoester ; Libai Huang
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：October 30, 2014
• 年：2014
• 卷：118
• 期：43
• 页码：24854-24865
• 全文大小：596K
• ISSN：1932-7455

文摘

We present an account of the optical properties of the Frenkel excitons in self-assembled porphyrin tubular aggregates that represent an analog to natural photosynthetic antennae. Using a combination of ultrafast optical spectroscopy and stochastic exciton modeling, we address both linear and nonlinear exciton absorption, relaxation pathways, and the role of disorder. The static disorder-dominated absorption and fluorescence line widths show little temperature dependence for the lowest excitons (Q band), which we successfully simulate using a model of exciton scattering on acoustic phonons in the host matrix. Temperature-dependent transient absorption of and fluorescence from the excitons in the tubular aggregates are marked by nonexponential decays with time scales ranging from a few picoseconds to a few nanoseconds, reflecting complex relaxation mechanisms. Combined experimental and theoretical investigations indicate that nonradiative pathways induced by traps and defects dominate the relaxation of excitons in the tubular aggregates. We model the pump鈥損robe spectra and ascribe the excited-state absorption to transitions from one-exciton states to a manifold of mixed one- and two-exciton states. Our results demonstrate that while the delocalized Frenkel excitons (over 208 (1036) molecules for the optically dominant excitons in the Q (B) band) resulting from strong intermolecular coupling in these aggregates could potentially facilitate efficient energy transfer, fast relaxation due to defects and disorder probably present a major limitation for exciton transport over large distances.