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Schultz, Thomas
CRASY (Correlated Rotational Alignment Spectroscopy)
Research Interests
  • Correlated spectroscopy
  • Ultrafast spectroscopy
  • High-resolution spectroscopy
  • Photochemistry

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Efficient deactivation of a model base pair via excited-state hydrogen transfer

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Title
Efficient deactivation of a model base pair via excited-state hydrogen transfer
Author
Schultz, ThomasSamoylova, E.Radloff, W.Hertel, I.V.Sobolewski, A.L.Domcke, W.
Issue Date
2004-12
Publisher
AMER ASSOC ADVANCEMENT SCIENCE
Citation
SCIENCE, v.306, no.5702, pp.1765 - 1768
Abstract
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.
URI
https://scholarworks.unist.ac.kr/handle/201301/6267
URL
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=10044281511
DOI
10.1126/science.1104038
ISSN
0036-8075
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CHM_Journal Papers
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