FTIR DETECTION OF THE TERT-BUTYL HYDROPEROXIDE DIMER

Jensen, Casper Vindahl

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

Description

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

Genre of Resource

Conference Paper / Presentation

Language

eng

Handle URL

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

DOI

https://doi.org/10.15278/isms.2023.6788

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