Efficient deactivation of a model base pair via excited-state hydrogen transfer
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- Efficient deactivation of a model base pair via excited-state hydrogen transfer
- Schultz, Thomas; Samoylova, E.; Radloff, W.; Hertel, I.V.; Sobolewski, A.L.; Domcke, W.
- AB-INITIO; ELECTRONIC-SPECTRA; CYTOSINE; GUANINE; 2-AMINOPYRIDINE; DYNAMICS; DECAY
- Issue Date
- AMER ASSOC ADVANCEMENT SCIENCE
- SCIENCE, v.306, no.5702, pp.1765 - 1768
- We present experimental and theoretical evidence for an excited-state deactivation mechanism specific to hydrogen-bonded aromatic dimers, which may account, in part, for the photostability of the Watson-Crick base pairs in DNA. Femtosecond time-resolved mass spectroscopy of 2-aminopyridine clusters reveals an excited-state lifetime of 65 ± 10 picoseconds for the near-planar hydrogen-bonded dimer, which is significantly shorter than the lifetime of either the monomer or the 3- and 4-membered nonplanar clusters. Ab initio calculations of reaction pathways and potential-energy profiles identify the mechanism of the enhanced excited-state decay of the dimer: Conical intersections connect the locally excited 1ππ* state and the electronic ground state with a 1ππ* charge-transfer state that is strongly stabilized by the transfer of a proton.
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