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Abstract
Hydrogen-bonded gas-phase molecular clusters of dihydrogen trioxide (HOOOH) have been investigated
using DFT (B3LYP/6-311++G(3df,3pd)) and MP2/6-311++G(3df,3pd) methods. The binding energies,
vibrational frequencies, and dipole moments for the various dimer, trimer, and tetramer structures, in which
HOOOH acts as a proton donor as well as an acceptor, are reported. The stronger binding interaction in the
HOOOH dimer, as compared to that in the analogous cyclic structure of the HOOH dimer, indicates that
dihydrogen trioxide is a stronger acid than hydrogen peroxide. A new decomposition pathway for HOOOH
was explored. Decomposition occurs via an eight-membered ring transition state for the intermolecular (slightly
asynchronous) transfer of two protons between the HOOOH molecules, which form a cyclic dimer, to produce
water and singlet oxygen (Δ1O2). This autocatalytic decomposition appears to explain a relatively fast
decomposition (ΔHa(298K) ) 19.9 kcal/mol, B3LYP/6-311+G(d,p)) of HOOOH in nonpolar (inert) solvents,
which might even compete with the water-assisted decomposition of this simplest of polyoxides (ΔHa(298K)
) 18.8 kcal/mol for (H2O)2-assisted decomposition) in more polar solvents. The formation of relatively strongly
hydrogen-bonded complexes between HOOOH and organic oxygen bases, HOOOH-B (B ) acetone and
dimethyl ether), strongly retards the decomposition in these bases as solvents, most likely by preventing such
a proton transfer.
Original language | English |
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Pages (from-to) | 8129-8135 |
Number of pages | 6 |
Journal | Journal of Physical Chemistry A |
Volume | 112 |
Issue number | 35 |
DOIs | |
Publication status | Published - 4 Sep 2008 |
Keywords
- Dihydrogen Trioxide Clusters
- (HOOOH)n (n = 2−4)
- Hydrogen-Bonded Complexes
- HOOOH
- Acetone
- Dimethyl Ether
- Implications
- Decomposition
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Projects
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