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Photodissociation of pyrene dimer radical cation during the pulse radiolysis–laser flash photolysis combined method

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Abstract

Photodissociation of pyrene (Py) dimer radical cation (Py ∙+2 ) giving pyrene radical cation (Py∙+) and Py and subsequent regeneration of Py ∙+2 by association of Py∙+ and Py were directly observed during the pulse radiolysis–laser flash photolysis combined method at room temperature. When Py ∙+2 was excited at the local excitation band with the 532-nm laser flash, the rapid growth and decay of monomeric Py∙+ were observed at 460 nm. The dissociation of Py ∙+2 proceeded via a one-photon process to give the ground-state Py∙+(D0) and Py in the quantum yield (Φdiss) of (2.9 ± 0.9) × 10−3. It was shown that Py∙+ decayed with a time constant of several tens of nanoseconds, indicating that the association of Py∙+ with Py regenerating Py ∙+2 proceeds at a diffusion-controlled rate. The photodissociation proceeded from the lowest excited state of Py ∙+2 , even when Py ∙+2 was excited to the higher excited state. The difference between the Φdiss value of Py ∙+2 and that previously reported for naphthalene dimer radical cation (Np ∙+2 ) is discussed.

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Acknowledgments

We thank the members of the Research Laboratory for Quantum Beam Science of SANKEN, Osaka University, for running the linear accelerator. This work has been partly supported by a Grant-in-Aid for Scientific Research [Project 21350075, 22245022, Priority Area (477), and others] from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japanese Government. T.M. thanks the WCU (World Class University) program funded by the Ministry of Education, Science and Technology through the National Research Foundation of Korea (R31-2008-10035-0) for the support.

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  1. The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka, 567-0047, Japan

    Shingo Samori, Mamoru Fujitsuka & Tetsuro Majima

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  1. Shingo Samori
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  2. Mamoru Fujitsuka
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  3. Tetsuro Majima
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Correspondence to Mamoru Fujitsuka or Tetsuro Majima.

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Samori, S., Fujitsuka, M. & Majima, T. Photodissociation of pyrene dimer radical cation during the pulse radiolysis–laser flash photolysis combined method. Res Chem Intermed 39, 449–461 (2013). https://doi.org/10.1007/s11164-012-0662-2

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