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Title: Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH)

Abstract

Infrared (IR) action spectroscopy is utilized to characterize a prototypical carbon-centered hydroperoxyalkyl radical (•QOOH) transiently formed in the oxidation of volatile organic compounds. The •QOOH radical formed in isobutane oxidation, 2-hydroperoxy-2-methylprop-1-yl, •CH2(CH3)2COOH, is generated in the laboratory by H-atom abstraction from tert-butyl hydroperoxide (TBHP). IR spectral features of jet-cooled and stabilized •QOOH radicals are observed from 2950 to 7050 cm–1 at energies that lie below and above the transition state barrier leading to OH radical and cyclic ether products. The observed •QOOH features include overtone OH and CH stretch transitions, combination bands involving OH or CH stretch and a lower frequency mode, and fundamental OH and CH stretch transitions. Most features arise from a single vibrational transition with band contours well simulated at a rotational temperature of 10 K. In each case, the OH products resulting from unimolecular decay of vibrationally activated •QOOH are detected by UV laser-induced fluorescence. Assignments of observed •QOOH IR transitions are guided by anharmonic frequencies computed using second order vibrational perturbation theory, a 2 + 1 model that focuses on the coupling of the OH stretch with two low-frequency torsions, as well as recently predicted statistical •QOOH unimolecular decay rates that include heavy-atom tunneling. Mostmore » of the observed vibrational transitions of •QOOH are readily distinguished from those of the TBHP precursor. Furthermore, the distinctive IR transitions of •QOOH, including the strong fundamental OH stretch, provide a general means for detection of •QOOH under controlled laboratory and real-world conditions.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Univ. of Washington, Seattle, WA (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Independent Research Fund Denmark; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Carlsberg Foundation; USDOE
OSTI Identifier:
1880795
Alternate Identifier(s):
OSTI ID: 1838085
Grant/Contract Number:  
AC02-06CH11357; FG02-87ER13792; ACI-1548562; SC0021081; OAC-1663636; CHE-1624430; CF18-0614; 9036-00016B
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 156; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Action spectroscopy; Perturbation theory; Transition state; Isomerization; Multiphoton excitation; Laser induced fluorescence

Citation Formats

Hansen, Anne S., Bhagde, Trisha, Qian, Yujie, Cavazos, Alyssa, Huchmala, Rachel M., Boyer, Mark A., Gavin-Hanner, Coire F., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH). United States: N. p., 2022. Web. doi:10.1063/5.0076505.
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Hansen, Anne S., Bhagde, Trisha, Qian, Yujie, Cavazos, Alyssa, Huchmala, Rachel M., Boyer, Mark A., Gavin-Hanner, Coire F., Klippenstein, Stephen J., McCoy, Anne B., & Lester, Marsha I. Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH). United States. https://doi.org/10.1063/5.0076505
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Hansen, Anne S., Bhagde, Trisha, Qian, Yujie, Cavazos, Alyssa, Huchmala, Rachel M., Boyer, Mark A., Gavin-Hanner, Coire F., Klippenstein, Stephen J., McCoy, Anne B., and Lester, Marsha I. Mon . "Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH)". United States. https://doi.org/10.1063/5.0076505. https://www.osti.gov/servlets/purl/1880795.
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@article{osti_1880795,
title = {Infrared spectroscopic signature of a hydroperoxyalkyl radical (•QOOH)},
author = {Hansen, Anne S. and Bhagde, Trisha and Qian, Yujie and Cavazos, Alyssa and Huchmala, Rachel M. and Boyer, Mark A. and Gavin-Hanner, Coire F. and Klippenstein, Stephen J. and McCoy, Anne B. and Lester, Marsha I.},
abstractNote = {Infrared (IR) action spectroscopy is utilized to characterize a prototypical carbon-centered hydroperoxyalkyl radical (•QOOH) transiently formed in the oxidation of volatile organic compounds. The •QOOH radical formed in isobutane oxidation, 2-hydroperoxy-2-methylprop-1-yl, •CH2(CH3)2COOH, is generated in the laboratory by H-atom abstraction from tert-butyl hydroperoxide (TBHP). IR spectral features of jet-cooled and stabilized •QOOH radicals are observed from 2950 to 7050 cm–1 at energies that lie below and above the transition state barrier leading to OH radical and cyclic ether products. The observed •QOOH features include overtone OH and CH stretch transitions, combination bands involving OH or CH stretch and a lower frequency mode, and fundamental OH and CH stretch transitions. Most features arise from a single vibrational transition with band contours well simulated at a rotational temperature of 10 K. In each case, the OH products resulting from unimolecular decay of vibrationally activated •QOOH are detected by UV laser-induced fluorescence. Assignments of observed •QOOH IR transitions are guided by anharmonic frequencies computed using second order vibrational perturbation theory, a 2 + 1 model that focuses on the coupling of the OH stretch with two low-frequency torsions, as well as recently predicted statistical •QOOH unimolecular decay rates that include heavy-atom tunneling. Most of the observed vibrational transitions of •QOOH are readily distinguished from those of the TBHP precursor. Furthermore, the distinctive IR transitions of •QOOH, including the strong fundamental OH stretch, provide a general means for detection of •QOOH under controlled laboratory and real-world conditions.},
doi = {10.1063/5.0076505},
journal = {Journal of Chemical Physics},
number = 1,
volume = 156,
place = {United States},
year = {Mon Jan 03 00:00:00 EST 2022},
month = {Mon Jan 03 00:00:00 EST 2022}
}
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Works referenced in this record:

Anharmonic vibrational properties by a fully automated second-order perturbative approach
journal, January 2005

  • Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 122, Issue 1
  • DOI: 10.1063/1.1824881

Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance
journal, January 2012

  • Orlando, John J.; Tyndall, Geoffrey S.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35166h

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry
journal, May 2017

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes
journal, February 2016

Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors
journal, May 2010

  • Sharma, Sandeep; Raman, Sumathy; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 18
  • DOI: 10.1021/jp9098792

UV Spectroscopic Characterization of Dimethyl- and Ethyl-Substituted Carbonyl Oxides
journal, March 2014

  • Liu, Fang; Beames, Joseph M.; Green, Amy M.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 12
  • DOI: 10.1021/jp412726z

High-level theoretical characterization of the vinoxy radical ( • CH 2 CHO) + O 2 reaction
journal, May 2018

  • Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.
  • The Journal of Chemical Physics, Vol. 148, Issue 18
  • DOI: 10.1063/1.5026295

Chain Branching and Termination in the Low-Temperature Combustion of n -Alkanes: 2-Pentyl Radical + O 2 , Isomerization and Association of the Second O 2
journal, July 2010

  • Asatryan, Rubik; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 29
  • DOI: 10.1021/jp101159h

Experimental and Modeling Studies of the Pressure and Temperature Dependences of the Kinetics and the OH Yields in the Acetyl + O 2 Reaction
journal, February 2011

  • Carr, Scott A.; Glowacki, David R.; Liang, Chi-Hsiu
  • The Journal of Physical Chemistry A, Vol. 115, Issue 6
  • DOI: 10.1021/jp1099199

Watching a hydroperoxyalkyl radical (•QOOH) dissociate
journal, August 2021

Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)
journal, February 2015

Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes
journal, March 2016

Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O 2
journal, February 2012

  • Crounse, John D.; Knap, Hasse C.; Ørnsø, Kristian B.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 24
  • DOI: 10.1021/jp211560u

Unconventional Peroxy Chemistry in Alcohol Oxidation: The Water Elimination Pathway
journal, January 2013

  • Welz, Oliver; Klippenstein, Stephen J.; Harding, Lawrence B.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
  • DOI: 10.1021/jz302004w

UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH 3 CHOO
journal, June 2013

  • Beames, Joseph M.; Liu, Fang; Lu, Lu
  • The Journal of Chemical Physics, Vol. 138, Issue 24
  • DOI: 10.1063/1.4810865

Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH 2 OO
journal, December 2012

  • Beames, Joseph M.; Liu, Fang; Lu, Lu
  • Journal of the American Chemical Society, Vol. 134, Issue 49
  • DOI: 10.1021/ja310603j

Coupling of torsion and OH-stretching in tert -butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum
journal, April 2021

  • Hansen, Anne S.; Huchmala, Rachel M.; Vogt, Emil
  • The Journal of Chemical Physics, Vol. 154, Issue 16
  • DOI: 10.1063/5.0048020

Characterization of the 2-methylvinoxy radical + O 2 reaction: A focal point analysis and composite multireference study
journal, September 2019

  • Davis, Matthew M.; Weidman, Jared D.; Abbott, Adam S.
  • The Journal of Chemical Physics, Vol. 151, Issue 12
  • DOI: 10.1063/1.5113800

Coupling of torsion and OH-stretching in tert -butyl hydroperoxide. II. The OH-stretching fundamental and overtone spectra
journal, April 2021

  • Vogt, Emil; Huchmala, Rachel M.; Jensen, Casper V.
  • The Journal of Chemical Physics, Vol. 154, Issue 16
  • DOI: 10.1063/5.0048022

Vibrationally mediated photodissociation of t ‐butyl hydroperoxide: Vibrational overtone spectroscopy and photodissociation dynamics
journal, June 1989

  • Likar, M. D.; Baggott, J. E.; Crim, F. F.
  • The Journal of Chemical Physics, Vol. 90, Issue 11
  • DOI: 10.1063/1.456343

̇QOOH-mediated reactions in cyclohexene oxidation
journal, January 2019

  • Koritzke, Alanna L.; Davis, Jacob C.; Caravan, Rebecca L.
  • Proceedings of the Combustion Institute, Vol. 37, Issue 1
  • DOI: 10.1016/j.proci.2018.05.029

Kinetics of elementary reactions in low-temperature autoignition chemistry
journal, August 2011

  • Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X.
  • Progress in Energy and Combustion Science, Vol. 37, Issue 4
  • DOI: 10.1016/j.pecs.2010.06.006

Kinetic Study on Reactions of 1- and 2-Methylvinoxy Radicals with O 2
journal, January 2001

  • Oguchi, Tatsuo; Miyoshi, Akira; Koshi, Mitsuo
  • The Journal of Physical Chemistry A, Vol. 105, Issue 2
  • DOI: 10.1021/jp001826q

Vibrationally mediated photodissociation of hydrogen peroxide
journal, November 1987

  • Ticich, T. M.; Likar, M. D.; Dübal, H. ‐R.
  • The Journal of Chemical Physics, Vol. 87, Issue 10
  • DOI: 10.1063/1.453735

Direct Observation of Aliphatic Peroxy Radical Autoxidation and Water Effects: An Experimental and Theoretical Study
journal, August 2019

  • Nozière, Barbara; Vereecken, Luc
  • Angewandte Chemie International Edition, Vol. 58, Issue 39
  • DOI: 10.1002/anie.201907981

A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method
journal, February 1992

  • Colbert, Daniel T.; Miller, William H.
  • The Journal of Chemical Physics, Vol. 96, Issue 3
  • DOI: 10.1063/1.462100

Role of O 2 + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients
journal, March 2012

  • Goldsmith, C. Franklin; Green, William H.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 13
  • DOI: 10.1021/jp210722w

Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products
journal, September 2014

Direct observation of unimolecular decay of CH 3 CH 2 CHOO Criegee intermediates to OH radical products
journal, July 2016

  • Fang, Yi; Liu, Fang; Klippenstein, Stephen J.
  • The Journal of Chemical Physics, Vol. 145, Issue 4
  • DOI: 10.1063/1.4958992

High-resolution diode laser absorption spectroscopy of the O–H stretch overtone band (2,0,0)←(0,0,0) of the HO2 radical
journal, May 2003

Communication: Real time observation of unimolecular decay of Criegee intermediates to OH radical products
journal, February 2016

  • Fang, Yi; Liu, Fang; Barber, Victoria P.
  • The Journal of Chemical Physics, Vol. 144, Issue 6
  • DOI: 10.1063/1.4941768

A theoretical study of cyclic ether formation reactions
journal, January 2017

  • Bugler, John; Power, Jennifer; Curran, Henry J.
  • Proceedings of the Combustion Institute, Vol. 36, Issue 1
  • DOI: 10.1016/j.proci.2016.05.006

Analysis of Tertiary Butyl Radical + O 2 , Isobutene + HO 2 , Isobutene + OH, and Isobutene−OH Adducts + O 2 :  A Detailed Tertiary Butyl Oxidation Mechanism
journal, December 1999

  • Chen, Chiung-Ju; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 48
  • DOI: 10.1021/jp991227n

(CH3)3COOH (tert-butyl hydroperoxide): OH reaction rate coefficients between 206 and 375 K and the OH photolysis quantum yield at 248 nm
journal, January 2010

  • Baasandorj, Munkhbayar; Papanastasiou, Dimitrios K.; Talukdar, Ranajit K.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 38
  • DOI: 10.1039/c0cp00463d

Direct production of OH radicals upon CH overtone activation of (CH 3 ) 2 COO Criegee intermediates
journal, December 2014

  • Liu, Fang; Beames, Joseph M.; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 141, Issue 23
  • DOI: 10.1063/1.4903961

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Temperature and Pressure Dependent Kinetics of QOOH Decomposition and Reaction with O 2 : Experimental and Theoretical Investigations of QOOH Radicals Derived from Cl + (CH 3 ) 3 COOH
journal, October 2019

  • Whelan, Charlotte A.; Blitz, Mark A.; Shannon, Robin
  • The Journal of Physical Chemistry A, Vol. 123, Issue 47
  • DOI: 10.1021/acs.jpca.9b08785

The fate of the tert-butyl radical in low-temperature autoignition reactions
journal, May 2017

  • Moore, Kevin B.; Turney, Justin M.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 146, Issue 19
  • DOI: 10.1063/1.4983128

Trends in organic hydroperoxide photodissociation and absorption cross sections between 266 and 377 nm
journal, January 2014

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