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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28 April 2021
Research Article|
April 27 2021
Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum
Special Collection:
Special Collection in Honor of Women in Chemical Physics and Physical Chemistry
Anne S. Hansen
;
Anne S. Hansen
1
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104-6323, USA
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Rachel M. Huchmala
;
Rachel M. Huchmala
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195-1700, USA
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Emil Vogt
;
Emil Vogt
3
Department of Chemistry, University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen, Denmark
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Mark A. Boyer
;
Mark A. Boyer
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195-1700, USA
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Trisha Bhagde
;
Trisha Bhagde
1
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104-6323, USA
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Michael F. Vansco
;
Michael F. Vansco
1
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104-6323, USA
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Casper V. Jensen
;
Casper V. Jensen
3
Department of Chemistry, University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen, Denmark
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Alexander Kjærsgaard
;
Alexander Kjærsgaard
3
Department of Chemistry, University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen, Denmark
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Henrik G. Kjaergaard
;
Henrik G. Kjaergaard
a)
3
Department of Chemistry, University of Copenhagen
, Universitetsparken 5, DK-2100 Copenhagen, Denmark
a)Authors to whom correspondence should be addressed: hgk@chem.ku.dk; abmccoy@uw.edu; and milester@sas.upenn.edu
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Anne B. McCoy
;
Anne B. McCoy
a)
2
Department of Chemistry, University of Washington
, Seattle, Washington 98195-1700, USA
a)Authors to whom correspondence should be addressed: hgk@chem.ku.dk; abmccoy@uw.edu; and milester@sas.upenn.edu
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Marsha I. Lester
Marsha I. Lester
a)
1
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104-6323, USA
a)Authors to whom correspondence should be addressed: hgk@chem.ku.dk; abmccoy@uw.edu; and milester@sas.upenn.edu
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a)Authors to whom correspondence should be addressed: hgk@chem.ku.dk; abmccoy@uw.edu; and milester@sas.upenn.edu
Note: This paper is part of the JCP Special Collection in Honor of Women in Chemical Physics and Physical Chemistry.
J. Chem. Phys. 154, 164306 (2021)
Article history
Received:
February 18 2021
Accepted:
March 23 2021
Connected Content
A companion article has been published:
Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. II. The OH-stretching fundamental and overtone spectra
Citation
Anne S. Hansen, Rachel M. Huchmala, Emil Vogt, Mark A. Boyer, Trisha Bhagde, Michael F. Vansco, Casper V. Jensen, Alexander Kjærsgaard, Henrik G. Kjaergaard, Anne B. McCoy, Marsha I. Lester; Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum. J. Chem. Phys. 28 April 2021; 154 (16): 164306. https://doi.org/10.1063/5.0048020
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