The 351.1 nm photoelectron spectrum of the peroxyacetate anion,
(CH3C(O)OO−) was measured. Analysis of the spectrum
shows that the observed spectral features arise almost exclusively from
transitions between the trans-conformer of the anion and the
X˜22A″ and
Ã2A′ states of the corresponding radical. The
electron affinity of trans-CH3C(O)OO is 2.381 ±
0.007 eV and the term energy splitting of the Ã2A′
state is 0.691 ± 0.009 eV, in excellent agreement with two prior values
[Zalyubovsky et al. J. Phys. Chem. A 107, 7704 (2003); Hu
et al. J. Phys. Chem. 124, 114305/1 (2006); Hu et
al. J. Phys. Chem. 110, 2629 (2006)]. The gas-phase acidity of
trans-peroxyacetic acid was bracketed between the acidity
of acetic acid and tert-butylthiol at
ΔaG298(trans-CH3C(O)OOH)
= 1439 ± 14 kJ mol−1 and
ΔaH298(trans-CH3C(O)
OOH) = 1467 ± 14 kJ mol−1. The acidity of
cis-CH3C(O)OOH was found by adding a calculated
energy correction to the acidity of the trans-conformer;
ΔaG298[cis-CH3C(O)OOH]
= 1461 ± 14 kJ mol−1 and
ΔaH298[cis-CH3C(O)OOH]
= 1490 ± 14 kJ mol−1. The O–H bond dissociation energies for both
conformers were determined using a negative ion thermodynamic cycle to be
D0[trans-CH3C(O)OOH]
= 381 ± 14 kJ mol−1 and
D0[cis-CH3C(O)OOH] =
403±14 kJ mol−1. The atmospheric implications of these results and
relations to the thermochemistry of peroxyacetyl nitrate are discussed
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