Non-radiative decay paths in rhodamines: new theoretical insights

Literature Information

Publication Date 2014-07-14
DOI 10.1039/C4CP02622E
Impact Factor 3.676
Authors

Umberto Raucci, Paolo A. Netti, Ilaria Ciofini


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Abstract

We individuate a photoinduced electron transfer (PeT) as a quenching mechanism affecting rhodamine B photophysics in solvent. The PeT involves an electron transfer from the carboxylate group to the xanthene ring of rhodamine B. This is finely modulated by the subtle balance of coulombic and non-classical interactions between the carboxyphenyl and xanthene rings, also mediated by the solvent. We propose the use of an electronic density based index, the so called DCT index, as a new tool to assess and quantify the nature of the excited states involved in non-radiative decays near the region of their intersection. In the present case, this analysis allows us to gain insight on the interconversion process from the bright state to the dark state responsible for the quenching of rhodamine B fluorescence. Our findings encourage the use of density based indices to study the processes affecting excited state reactions that are characterized by a drastic change in the excitation nature, in order to rationalize the photophysical behavior of complex molecular systems.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 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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