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  • Ultrafast 2D IR spectroscop...
    Thämer, Martin; De Marco, Luigi; Ramasesha, Krupa; Mandal, Aritra; Tokmakoff, Andrei

    Science (American Association for the Advancement of Science), 10/2015, Volume: 350, Issue: 6256
    Journal Article

    Despite decades of study, the structures adopted to accommodate an excess proton in water and the mechanism by which they interconvert remain elusive. We used ultrafast two-dimensional infrared (2D IR) spectroscopy to investigate protons in aqueous hydrochloric acid solutions. By exciting O–H stretching vibrations and detecting the spectral response throughout the mid-IR region, we observed the interaction between the stretching and bending vibrations characteristic of the flanking waters of the Zundel complex, H(H2O)2+, at 3200 and 1760 cm–1, respectively. From time-dependent shifts of the stretch-bend cross peak, we determined a lower limit on the lifetime of this complex of 480 femtoseconds. These results suggest a key role for the Zundel complex in aqueous proton transfer.