1 research outputs found
UV Photochemistry of Peroxyformic Acid (HC(O)OOH): An Experimental and Computational Study Investigating 355 nm Photolysis
The photochemistry of peroxyformic
acid (PFA), a molecule of atmospheric
interest exhibiting internal hydrogen bonding, is examined by exciting
the molecule at 355 nm and detecting the nascent OH fragments using
laser-induced fluorescence. The OH radicals are found to be formed
in their ground electronic state with the vast majority of available
energy appearing in fragment translation. The OH fragments are vibrationally
cold (v″ = 0) with only modest rotational excitation. The average
rotational energy is determined to be 0.35 kcal/mol. Further, the
degree of OH rotational excitation from PFA is found to be significantly
less than that arising from the dissociation of H<sub>2</sub>O<sub>2</sub> as well as other hydroperoxides over the same wavelength.
Ab initio calculation at the EOM-CCSD level is used to investigate
the first few electronic excited states of PFA. Differences in the
computed torsional potential between PFA and H<sub>2</sub>O<sub>2</sub> help rationalize the observed variation in their respective OH fragment
rotational excitation. The calculations also establish that the electronic
excited state of PFA accessed in the near UV is of <sup>1</sup>A″
symmetry and involves a σ*<sub>(O–O)</sub> ← n<sub>(O)</sub> excitation. Additionally, the UV absorption cross section
of PFA at 355 and 282 nm is estimated by comparing the yield of OH
from PFA at these wavelengths to that from hydrogen peroxide for which
the absorption cross sections is known