FTIR DETECTION OF THE TERT-BUTYL HYDROPEROXIDE DIMER

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https://hdl.handle.net/2142/122469

Title: FTIR DETECTION OF THE TERT-BUTYL HYDROPEROXIDE DIMER
Author(s): Jensen, Casper Vindahl
Contributor(s): Kjaergaard, Henrik G.
Issue Date: 2023-06-20
Keyword(s): Clusters/Complexes
Abstract: We have detected the tert-butyl hydroperoxide dimer (t-BuOOH)₂ in gas phase at room temperature using conventional FTIR techniques. The dimer is identified by an asymmetric absorbance band assigned to the hydrogen-bound OHb-stretch. The gas-phase dimer assignment is supported by Ar matrix isolation FTIR experiments at 12 K. The dimer OHb-stretching band is located at ∼3452 cm−¹ redshifted by ∼145 cm−¹ from the monomer OH-stretching band. Theoretically, we find the lowest energy structure of (t-BuOOH)₂ to be a doubly hydrogen-bound 6-membered ring. The ring strain in this structure leads to non-optimal H-bond angles and a smaller than expected redshift. We calculate the transition frequency and oscillator strength of the OHb-stretching transition with a 1D local mode model and DFT electronic structure methods. The constant of dimer formation K is estimated from the experimental integrated absorbance and the theoretically calculated oscillator strength of the OHb-stretching band. The unitless K is estimated to be ∼0.41 for (t-BuOOH)₂.
Publisher: International Symposium on Molecular Spectroscopy
Type of Resource: Text
Language: eng
Handle URL: https://hdl.handle.net/2142/122469
DOI: https://doi.org/10.15278/isms.2023.6788