Gas-Phase Room-Temperature Detection of the tert-Butyl Hydroperoxide Dimer
Research output: Contribution to journal › Journal article › Research › peer-review
We have detected the tert-butyl hydroperoxide dimer, (t-BuOOH)2, in the gas phase at room temperature using conventional FTIR techniques. The dimer is identified by an asymmetric absorbance band assigned to the fundamental hydrogen-bound OHb-stretch. The weighted band maximum of the dimer OHb-stretch is located at ∼3452 cm–1, red-shifted by ∼145 cm–1 from the monomer OH-stretching band. The gas-phase dimer assignment is supported by Ar matrix isolation FTIR experiments at 12 K and experiments with a partially deuterated sample. Computationally, we find the lowest energy structure of (t-BuOOH)2 to be a doubly hydrogen bound six-membered ring with non-optimal hydrogen bond angles. We estimate the gas-phase constant of dimer formation, K, to be 0.4 (standard pressure of 1 bar) using the experimental integrated absorbance and a theoretically determined oscillator strength of the OHb-stretching band.
Original language | English |
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Journal | Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory |
Volume | 127 |
Issue number | 31 |
Pages (from-to) | 6476-6485 |
Number of pages | 10 |
ISSN | 1089-5639 |
DOIs | |
Publication status | Published - 2023 |
ID: 362803517