Document Detail


Excited-State Double Proton Transfer of 7-Azaindole Dimers in a Low-Temperature Organic Glass.
MedLine Citation:
PMID:  21413991     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The excited-state double proton transfer of model DNA base pairs, 7-azaindole dimers, is explored in a low-temperature organic glass of n-dodecane using picosecond time-resolved fluorescence spectroscopy. Reaction mechanisms are found to depend on the conformations of 7-azaindole dimers at the moment of excitation; whereas planar conformers tautomerize rapidly (<10 ps), twisted conformers undergo double proton transfer to form tautomeric dimers on the time scale of 250 ps at 8 K. The proton transfer is found to consist of two orthogonal steps: precursor-configurational optimization and intrinsic proton transfer via tunneling. The rate is almost isotope-independent at cryogenic temperatures because configurational optimization is the rate-determining step of the overall proton transfer. This optimization is assisted by lattice vibrations below 150 K or by librational motions above 150 K.
Authors:
Hyeongtaek Lim; Sun-Young Park; Du-Jeon Jang
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2011-3-17
Journal Detail:
Title:  Photochemistry and photobiology     Volume:  -     ISSN:  1751-1097     ISO Abbreviation:  -     Publication Date:  2011 Mar 
Date Detail:
Created Date:  2011-3-18     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0376425     Medline TA:  Photochem Photobiol     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Journal compilation © 2011 American Society for Photobiology.
Affiliation:
School of Chemistry, Seoul National University, NS60, Seoul 151-747, Korea.
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