Two-dimensional electronic spectra of an aggregating dye: simultaneous measurement of monomeric and dimeric line-shapes

文献信息

发布日期 2009-05-18
DOI 10.1039/B902477H
影响因子 3.676
作者

Alexandra Nemeth, Vladimír Lukeš, Jaroslaw Sperling, Franz Milota, Tomáš Mančal


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摘要

We present a sequence of two-dimensional electronic spectra of a prototypical cyanine dye, whose spectral properties in aqueous solution are determined by the formation of a monomer–dimer equilibrium. Quantum-chemical methods are utilized to calculate the structure and absorption properties of the two species involved. Our spectroscopic results simultaneously characterize the spectral line-shapes of the two species in terms of underlying dynamic and static disorder, and demonstrate how the two-dimensional technique allows the exploitation of high spectral and temporal resolution in one and the same experiment. The distinctly different spectral relaxation dynamics are quantified in a two-dimensional line-shape analysis, by extracting the time dependent ratios of the diagonal and anti-diagonal peak-widths. Our findings are in line with theoretical considerations, that predict the fluctuational dynamics of an excitonic dimer state to be exchange-narrowed by excitation delocalization.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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