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• W2012206929 endingPage "14985" @default.
• W2012206929 startingPage "14985" @default.
• W2012206929 abstract "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." @default.
• W2012206929 created "2016-06-24" @default.
• W2012206929 creator A5036655135 @default.
• W2012206929 creator A5038448568 @default.
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• W2012206929 date "2010-01-01" @default.
• W2012206929 modified "2023-10-15" @default.
• W2012206929 title "First observation in the gas phase of the ultrafast electronic relaxation pathways of the S2 states of heme and hemin" @default.
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• W2012206929 doi "https://doi.org/10.1039/c0cp00687d" @default.
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