First observation in the gas phase of the ultrafast electronic relaxation pathways of the S2 states of heme and hemin
文献信息
Minh-Huong Ha-Thi, Niloufar Shafizadeh, Lionel Poisson, Benoit Soep
The time evolution of electronically excited heme (iron II protoporphyrin IX, [FeII PP]) and its associated salt hemin (iron III protoporphyrin IX chloride, [FeIII PP–Cl]), has been investigated for the first time in the gas phase by femtosecond pump–probe spectroscopy. The porphyrins were excited at 400 nm in the S2 state (Soret band) and their relaxation dynamics was probed by multiphoton ionization at 800 nm. This time evolution was compared with that of the excited state of zinc protoporphyrin IX [Zn PP] whose S2 excited state likely decays to the long lived S1 state through a conical intersection, in less than 100 fs. Instead, for [FeII PP] and [FeIII PP–Cl], the key relaxation step from S2 is interpreted as an ultrafast charge transfer from the porphyrin excited orbital π* to a vacant d orbital on the iron atom (ligand to metal charge transfer, LMCT). This intermediate LMCT state then relaxes to the ground state within 250 fs. Through this work a new, serendipitous, preparation step was found for FeII porphyrins, in the gas phase.
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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.




