Structure and dynamics of solvent shells around photoexcited metal complexes

Literature Information

Publication Date 2013-03-06
DOI 10.1039/C3CP44465A
Impact Factor 3.676
Authors

Jaroslaw J. Szymczak, Franziska D. Hofmann


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Abstract

Understanding the geometry, energetics and dynamics of solvated transition metal (TM) compounds is decisive in characterizing and optimizing their function. Here, we demonstrate that it is possible to quantify the structural dynamics of solvated [RuII(bpy)3], an important TM-complex for solar-energy harvesting research, by using state-of-the art force fields together with molecular simulations. Electronic excitation to [RuIII(bpy)3] leads to a nonequilibrium system in which excess energy is redistributed to the surrounding solvent following a cascade of dynamical effects that can be characterized by the simulations. The study reveals that the structure of the surrounding solvent relaxes towards the equilibrium on a sub-picosecond to a few-picosecond time scale. Analysis of solvent residence and rotational reorientation times during relaxation demonstrates increased dynamics in the inner solvation sphere on the picosecond time scale. Energy transfer to the solvent occurs on different time scales for the different degrees of freedom which range from a few hundred fs to several picoseconds.

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Back cover

2022-12-20 Cover

DOI: 10.1039/D3AN90004E

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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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