Proton-coupled hole transfer in X-irradiated doped crystalline cytosine.H2O.
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, assumedly by electron transfer. A huge deuterium kinetic isotope effect (KIE; >102-103) 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 A-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.
Krivokapić
André
A
Department of Physics, University of Oslo, P.O. Box 1048 Blindern, N-0316 Oslo 3, Norway. andre.krivokapic@fys.uio.no
Herak
Janko N
JN
Sagstuen
Einar
E
D003460:Crystallization; D003596:Cytosine / Q000031:analogs & derivatives / Q000737:chemistry*; D004579:Electron Transport; D007700:Kinetics; D011522:Protons; D013696:Temperature; D014867:Water / Q000737:chemistry*; D014965:X-Rays
D011522:Protons; D014867:Water; C058511:2-thiocytosine; D003596:Cytosine