Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 112, Issue 16, Pages 3597-3606Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp709855c
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Following exposure to X-irradiation at low temperatures, the main reactions taking place in single crystals of cytosine monohydrate doped with minute amounts of 2-thiocytosine are hole transfer (HT) from the electron-loss centers to the dopant and recombination of oxidation and reduction products, assurnedly by electron transfer. A huge deuterium kinetic isotope effect (KIE; > 10(2)-10(3)) at 100 K, together with the kinetic curves obtained and density functional theory (DFT) calculations of equilibrium energy changes, indicates that these reactions proceed through a concerted proton-coupled electron/hole transfer where the proton transfer occurs between hydrogen-bonded cytosine molecules. The temperature dependence of these reaction rates between 10 and 150 K in normal and partially deuterated samples was investigated by monitoring the growth and decay of the various radical species over time using electron paramagnetic resonance (EPR) spectroscopy. By assuming a random distribution of the hole donors and acceptors in the crystals, the data are consistent with an exponential distance-dependent rate, giving a distance decay constant (beta) around 1 angstrom(-1) for the HT, which indicates that a long-range single-step superexchange mechanism mediates the charge transfer. The reactions undergo a transition from a slow, weakly temperature-dependent rate to an Arrhenius-type rate at 40-50 K, presumably being activated by excitation of low-frequency intermolecular vibrations that couple to the process. Below this transition temperature, the transfer probability might be dominated by temperature-independent nuclear tunneling. A similar beta value in both temperature regions suggests that hopping is not activated.
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