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The Adiabatic Ionization Energy and Triplet T1 Energy of Jet-Cooled Keto-Amino Cytosine

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    Spectroscopy, Photochemistry, and Excited States

    The Adiabatic Ionization Energy and Triplet T1 Energy of Jet-Cooled Keto-Amino Cytosine
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    Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2012, 3, 23, 3576–3580
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    https://doi.org/10.1021/jz301719h
    Published November 19, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    Gas-phase cytosine exists in five different tautomer/rotamer forms 1, 2a, 2b, 3a, and 3b. We determine the threshold ionization energy (IE) of the keto-amino tautomer 1 as 8.73 ± 0.02 eV, using resonant two-photon ionization mass spectrometry in a supersonic molecular beam via the 1ππ* excited state. This is the first IE threshold measurement for the biologically relevant tautomer 1. The IE of the thermal gas-phase mixture of cytosine has been measured as 8.60 ± 0.05 eV by Kostko et al. using single-photon VUV photoionization [Phys. Chem. Chem. Phys., 2010, 12, 2860]. Given the tautomer distribution and ionization energies calculated in that work, our determination of the keto-amino tautomer IE implies that the IE measured by Kostko et al. is dominated by the enol-amino tautomers 2a and 2b. Upon excitation of keto-amino cytosine to its 1ππ* state, relaxation occurs to a lower-lying long-lived state. The IE threshold measured via this state places its energy about 0.69 eV below the 1ππ* state, in good agreement with the triplet T1 energy of keto-amino cytosine calculated by several high-level ab initio methods. The identification of keto-amino cytosine T1 is the basis for characterizing the intersystem crossing rates into and the photochemical reactions of this long-lived state.

    Copyright © 2012 American Chemical Society

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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2012, 3, 23, 3576–3580
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jz301719h
    Published November 19, 2012
    Copyright © 2012 American Chemical Society
    Request reuse permissions

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