Abstract
The photolysis of aqueous peroxynitrite, ONOO−(aq), by 266nm UV radiation is explored by femtosecond UV–UV and UV–IR transient absorption spectroscopies. The experiments show that 90±10% of the photolyzed ONOO− anions remain dissociated after 400ps. We analyze the photolysis in terms of five potential reaction channels, using steady-state absorption spectra together with electron structure calculations on potential photoproducts in clusters of water molecules. In addition, calculations of all excited electronic states of ONOO−(g) below the excitation energy help to explore the reaction channels. The dominant reaction channel is hν+ONOO−→O2•−+NO•.
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