Symmetry-Breaking Charge-Separation in a Subphthalocyanine Dimer Resolved by Two-Dimensional Electronic Spectroscopy

IF 3.3 3区 化学 Q2 CHEMISTRY, PHYSICAL
Giovanni Bressan, Isabelle Chambrier, Andrew N. Cammidge, Stephen R. Meech
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引用次数: 0

Abstract

Understanding the role of structural and environmental dynamics in the excited state properties of strongly coupled chromophores is of paramount importance in molecular photonics. Ultrafast, coherent, and multidimensional spectroscopies have been utilized to investigate such dynamics in the simplest model system, the molecular dimer. Here, we present a half-broadband two-dimensional electronic spectroscopy (HB2DES) study of the previously reported ultrafast symmetry-breaking charge separation (SB-CS) in the subphthalocyanine oxo-bridged homodimer μ-OSubPc2. Electronic structure calculations and 2D cross-peaks reveal the dimer’s excitonic structure, while ultrafast evolution of the multidimensional spectra unveils subtle features of structural relaxation, solvation dynamics, and inhomogeneous broadening in the SB-CS. Analysis of coherently excited vibrational motions reveals dimer-specific low-frequency Raman active modes coupled to higher-frequency vibrations localized on the SubPc cores. Finally, beatmap amplitude distributions characteristic of excitonic dimers with multiple bright states are reported and analyzed.

Abstract Image

二维电子光谱解析亚酞菁二聚体对称性破缺电荷分离
了解结构和环境动力学在强耦合发色团激发态特性中的作用在分子光子学中是至关重要的。超快、相干和多维光谱已被用于研究最简单的模型系统——分子二聚体中的这种动力学。本文利用半宽带二维电子谱(HB2DES)研究了先前报道的亚酞菁氧桥同二聚体μ-OSubPc2中的超快对称破缺电荷分离(sdb - cs)。电子结构计算和二维交叉峰揭示了二聚体的激子结构,而多维光谱的超快演化揭示了结构弛豫、溶剂化动力学和非均匀展宽等细微特征。对相干激发振动运动的分析揭示了二聚体特有的低频拉曼主动模式与SubPc核上的高频振动耦合。最后,报道并分析了多亮态激子二聚体的幅值分布特征。
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来源期刊
The Journal of Physical Chemistry C
The Journal of Physical Chemistry C 化学-材料科学:综合
CiteScore
6.50
自引率
8.10%
发文量
2047
审稿时长
1.8 months
期刊介绍: The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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