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Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non-Ergodic Behavior of Medium-Sized Ion Pairs?

Authors

  • Dr. Christopher J. Shaffer,

    1. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
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  • Dr. Ágnes Révész,

    1. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
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  • Dr. Detlef Schröder,

    Corresponding author
    1. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
    • Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
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  • Ing. Lukáš Severa,

    1. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
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  • Dr. Filip Teplý,

    1. Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
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  • Dr. Emilie-Laure Zins,

    1. Laboratoire de Dynamique, Interactions et Réactivité, UMR 7075 CNRS/UPMC, Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris 5 (France)
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  • Mgr. Lucie Jašíková,

    1. Department of Organic Chemistry, Charles University in Prague, Hlavova 8, 12843 Prague 2 (Czech Republic)
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  • Dr. Jana Roithová

    1. Department of Organic Chemistry, Charles University in Prague, Hlavova 8, 12843 Prague 2 (Czech Republic)
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  • This work was supported by the Academy of Sciences of the Czech Republic (RVO 61388963), the European Research Council (StG ISORI and AdG HORIZOMS), the Grant Agency of the Czech Republic (P207/10/2391), and the Ministry for Education, Youth, and Sports of the Czech Republic (MSM0021620857). We thank the staff of CLIO for assistance during the measurements and Lucie Bednarová and Pavel Fiedler for the IR measurements of the solid samples.

Abstract

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Communication breakdown: Ergodicity is the ability to predict the behavior of an ensemble from the behavior of its components. Infrared spectroscopy of mass-selected ion pairs in the gas phase suggests that intramolecular vibrational energy redistribution (IVR) is hindered in some of these noncovalently bound species, particularly when triflate anion is involved. The hindered IVR leads to a non-ergodic behavior on a timescale sufficient for the formation of new chemical bonds.

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