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Very Low Energy Electrons Transform the Cyclobutane‐Pyrimidine Dimer into a Highly Reactive Intermediate
Author(s) -
Edtbauer Achim,
Denifl Stephan,
Vizcaino Violaine,
An der Lan Lukas,
Russell Katherine,
Taubitz Jörg,
Wille Uta,
Feketeova Linda,
O'Hair Richard A. J.,
Märk Tilmann D.,
Illenberger Eugen,
Scheier Paul
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200900912
Subject(s) - pyrimidine dimer , cyclobutane , chemistry , thymine , electron , dimer , photochemistry , ion , atomic physics , dipole , molecule , dna , physics , dna damage , ring (chemistry) , biochemistry , organic chemistry , quantum mechanics
Electrons with virtually no kinetic energy (close to 0 eV) trigger the decomposition of cytotoxic cyclobutane‐pyrimidine dimer (CPD) into a surprisingly large variety of fragment ions plus their neutral counterparts. The response of CPD to low energy electrons is thus comparable to that of explosives like trinitrotoluene (TNT). The dominant unimolecular reaction is the splitting into two thymine like units, which can be considered as the essential molecular step in the photolyase of CPD. We find that CPD is significantly more sensitive towards low energy electrons than its thymine building blocks. It is proposed that electron attachment at very low energy proceeds via dipole bound states, supported by the large dipole moment of the molecule (6.2 D). These states act as effective doorways to dissociative electron attachment (DEA).