Coupling of torsion and OH-stretching in tert -butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum

Hansen, Anne S.; Huchmala, Rachel M.; Vogt, Emil; Boyer, Mark A.; Bhagde, Trisha; Vansco, Michael F.; Jensen, Casper V.; Kjærsgaard, Alexander; Kjaergaard, Henrik G.; McCoy, Anne B.; Lester, Marsha I.

doi:10.1063/5.0048020

Coupling of torsion and OH-stretching in tert -butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum

Journal Article · Tue Apr 27 00:00:00 EDT 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0048020· OSTI ID:1780162

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The infrared (IR) spectrum of tert-butyl hydroperoxide (TBHP) in the region of the first OH-stretching overtone has been observed under jet-cooled and thermal (300 K, 3 Torr) conditions at ∼7017 cm−1. The jet-cooled spectrum is recorded by IR multiphoton excitation with UV laser-induced fluorescence detection of OH radical products, while direct IR absorption is utilized under thermal conditions. Prior spectroscopic studies of TBHP and other hydroperoxides have shown that the OH-stretch and XOOH (X = H or C) torsion vibrations are strongly coupled, resulting in a double well potential associated with the torsional motion about the OO bond that is different for each of the OH-stretching vibrational states. A low barrier between the wells on the torsional potential results in tunneling split energy levels, which leads to four distinct transitions associated with excitation of the coupled OH-stretch-torsion states. In order to interpret the experimental results, two theoretical models are used that include the OH-stretch-torsion coupling in TBHP. Both methods are utilized to compute the vibrational transitions associated with the coupled OH-stretch-torsion states of TBHP, revealing the underlying transitions that compose the experimentally observed features. A comparison between theory and experiment illustrates the necessity for treatments that include OH-stretch and COOH torsion in order to unravel the spectral features observed in the first OH-stretching overtone region of TBHP.

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Sponsoring Organization:: USDOE

OSTI ID:: 1780162

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 154; ISSN 0021-9606

Publisher:: American Institute of PhysicsCopyright Statement

Country of Publication:: United States

Language:: English

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