Time-resolved dual fluorescence of 1-phenylpyrrole in acetonitrile: molecular dynamics simulations of solvent response to twisted intramolecular charge transfer
Literature Information
Jörn Manz, Boris Proppe, Burkhard Schmidt
The real-time dynamics of solvation of 1-phenylpyrrole (PhPy) in acetonitrile (ACN) upon electronic excitation is investigated by means of non-equilibrium molecular dynamics simulations. The interaction is modeled by empirical intermolecular pair potentials using partial charges and intramolecular torsional potentials from high level ab initio calculations of ground and excited states of PhPy. The intramolecular torsional motion following sudden excitation from the twisted ground state to the 2 1B charge transfer state is strongly damped by the viscous ACN solvent, leading to a near-exponential approach of the perpendicular conformation on a timescale of about 5–10 ps. The intermolecular dynamics is characterized by rapid reorientation of the solvent molecules on a timescale of 100 fs followed by weak quasi-coherent librations. The solvatochromic red-shift of the charge transfer state with respect to the locally excited 1 1B state results in dual fluorescence, thus supporting the twisted intramolecular charge transfer (TICT) mechanism for PhPy in a polar solvent.
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Physical Chemistry Chemical Physics

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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