TY - JOUR
T1 - Spectroscopy of the breaking bond
T2 - The diradical intermediate of the ring opening in oxazole
AU - Culberson, Lori M.
AU - Wallace, Adam A.
AU - Blackstone, Christopher C.
AU - Khuseynov, Dmitry
AU - Sanov, Andrei
PY - 2014/3/7
Y1 - 2014/3/7
N2 - Bond breaking is a challenging problem in both experimental and theoretical chemistry, due to the transient nature and multi-configurational electronic structure of dissociating molecules. We use anion photodetachment to probe the diradical interactions in the ring-opening reaction of oxazole and obtain a self-consistent picture of the breaking bond. Starting from the closed-shell cyclic molecule, the reaction is launched on the anion potential, as an attached electron cleaves a carbon-oxygen bond. In the photodetachment, two neutral potential regions are sampled. One corresponds to a completely dissociated bond, while the other-to the bond fragments separated by approximately 3 Å. At this chemically relevant distance, signatures of lingering through-space interactions between the radical centers are observed. This journal is
AB - Bond breaking is a challenging problem in both experimental and theoretical chemistry, due to the transient nature and multi-configurational electronic structure of dissociating molecules. We use anion photodetachment to probe the diradical interactions in the ring-opening reaction of oxazole and obtain a self-consistent picture of the breaking bond. Starting from the closed-shell cyclic molecule, the reaction is launched on the anion potential, as an attached electron cleaves a carbon-oxygen bond. In the photodetachment, two neutral potential regions are sampled. One corresponds to a completely dissociated bond, while the other-to the bond fragments separated by approximately 3 Å. At this chemically relevant distance, signatures of lingering through-space interactions between the radical centers are observed. This journal is
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U2 - 10.1039/c3cp54779e
DO - 10.1039/c3cp54779e
M3 - Article
AN - SCOPUS:84893637297
SN - 1463-9076
VL - 16
SP - 3964
EP - 3972
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 9
ER -