Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory

Abstract

Here, the photodissociation dynamics of the dimethyl-substituted acetone oxide Criegee intermediate [(CH3)2COO] is characterized following electronic excitation to the bright 1ππ* state, which leads to O (1D) + acetone [(CH3)2CO, S0] products. The UV action spectrum of (CH3)2COO recorded with O (1D) detection under jet-cooled conditions is broad, unstructured, and essentially unchanged from the corresponding electronic absorption spectrum obtained using a UV-induced depletion method. This indicates that UV excitation of (CH3)2COO leads predominantly to the O (1D) product channel. A higher energy O (3P) + (CH3)2CO (T1) product channel is not observed, although it is energetically accessible. In addition, complementary MS-CASPT2 trajectory surface-hopping (TSH) simulations indicate minimal population leading to the O (3P) channel and non-unity overall probability for dissociation (within 100 fs). Velocity map imaging of the O (1D) products is utilized to reveal the total kinetic energy release (TKER) distribution upon photodissociation of (CH3)2COO at various UV excitation energies. Simulation of the TKER distributions is performed using a hybrid model that combines an impulsive model with a statistical component, the latter reflecting the longer-lived (>100 fs) trajectories identified in the TSH calculations. The impulsive model accounts for vibrational activation of (CH3)2CO arising from geometrical changes between the Criegeemore » intermediate and the carbonyl product, indicating the importance of CO stretch, CCO bend, and CC stretch along with activation of hindered rotation and rock of the methyl groups in the (CH3)2CO product. Detailed comparison is also made with the TKER distribution arising from photodissociation dynamics of CH2OO upon UV excitation.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. University of Pennsylvania, Philadelphia, PA (United States)
  2. University of Louisiana at Lafayette, LA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1991924
Alternate Identifier(s):
OSTI ID: 1958882
Grant/Contract Number:  
FG02-87ER13792; ACI-1548562; CHE-2003422
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 25; Journal Issue: 10; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Karsili, Tolga V., and Lester, Marsha I. UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory. United States: N. p., 2023. Web. doi:10.1039/d3cp00207a.
Copy to clipboard
Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Karsili, Tolga V., & Lester, Marsha I. UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory. United States. https://doi.org/10.1039/d3cp00207a
Copy to clipboard
Wang, Guanghan, Liu, Tianlin, Zou, Meijun, Karsili, Tolga V., and Lester, Marsha I. Mon . "UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory". United States. https://doi.org/10.1039/d3cp00207a. https://www.osti.gov/servlets/purl/1991924.
Copy to clipboard
@article{osti_1991924,
title = {UV photodissociation dynamics of the acetone oxide Criegee intermediate: experiment and theory},
author = {Wang, Guanghan and Liu, Tianlin and Zou, Meijun and Karsili, Tolga V. and Lester, Marsha I.},
abstractNote = {Here, the photodissociation dynamics of the dimethyl-substituted acetone oxide Criegee intermediate [(CH3)2COO] is characterized following electronic excitation to the bright 1ππ* state, which leads to O (1D) + acetone [(CH3)2CO, S0] products. The UV action spectrum of (CH3)2COO recorded with O (1D) detection under jet-cooled conditions is broad, unstructured, and essentially unchanged from the corresponding electronic absorption spectrum obtained using a UV-induced depletion method. This indicates that UV excitation of (CH3)2COO leads predominantly to the O (1D) product channel. A higher energy O (3P) + (CH3)2CO (T1) product channel is not observed, although it is energetically accessible. In addition, complementary MS-CASPT2 trajectory surface-hopping (TSH) simulations indicate minimal population leading to the O (3P) channel and non-unity overall probability for dissociation (within 100 fs). Velocity map imaging of the O (1D) products is utilized to reveal the total kinetic energy release (TKER) distribution upon photodissociation of (CH3)2COO at various UV excitation energies. Simulation of the TKER distributions is performed using a hybrid model that combines an impulsive model with a statistical component, the latter reflecting the longer-lived (>100 fs) trajectories identified in the TSH calculations. The impulsive model accounts for vibrational activation of (CH3)2CO arising from geometrical changes between the Criegee intermediate and the carbonyl product, indicating the importance of CO stretch, CCO bend, and CC stretch along with activation of hindered rotation and rock of the methyl groups in the (CH3)2CO product. Detailed comparison is also made with the TKER distribution arising from photodissociation dynamics of CH2OO upon UV excitation.},
doi = {10.1039/d3cp00207a},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 10,
volume = 25,
place = {United States},
year = {Mon Feb 20 00:00:00 EST 2023},
month = {Mon Feb 20 00:00:00 EST 2023}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/d3cp00207a
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere
journal, January 2012

  • Vereecken, L.; Harder, H.; Novelli, A.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 42
  • DOI: 10.1039/c2cp42300f

Infrared identification of the Criegee intermediates syn- and anti-CH3CHOO, and their distinct conformation-dependent reactivity
journal, May 2015

  • Lin, Hui-Yu; Huang, Yu-Hsuan; Wang, Xiaohong
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8012

Identification of the ns σ and nd λ Rydberg states of O 2 for n =3–5
journal, November 1992

  • Yokelson, R. J.; Lipert, R. J.; Chupka, W. A.
  • The Journal of Chemical Physics, Vol. 97, Issue 9
  • DOI: 10.1063/1.463724

Detailed mechanism of the CH 2 I + O 2 reaction: Yield and self-reaction of the simplest Criegee intermediate CH 2 OO
journal, September 2014

  • Ting, Wei-Lun; Chang, Chun-Hung; Lee, Yu-Fang
  • The Journal of Chemical Physics, Vol. 141, Issue 10
  • DOI: 10.1063/1.4894405

A simple method for the evaluation of the second-order-perturbation energy from external double-excitations with a CASSCF reference wavefunction
journal, April 1982

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

UV absorption spectrum of the C2 Criegee intermediate CH 3 CHOO
journal, August 2014

  • Smith, Mica C.; Ting, Wei-Lun; Chang, Chun-Hung
  • The Journal of Chemical Physics, Vol. 141, Issue 7
  • DOI: 10.1063/1.4892582

Synthesis, Electronic Spectroscopy, and Photochemistry of Methacrolein Oxide: A Four-Carbon Unsaturated Criegee Intermediate from Isoprene Ozonolysis
journal, August 2019

  • Vansco, Michael F.; Marchetti, Barbara; Trongsiriwat, Nisalak
  • Journal of the American Chemical Society, Vol. 141, Issue 38
  • DOI: 10.1021/jacs.9b05193

Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH 2 OO
journal, October 2013

  • Lehman, Julia H.; Li, Hongwei; Beames, Joseph M.
  • The Journal of Chemical Physics, Vol. 139, Issue 14
  • DOI: 10.1063/1.4824655

Absolute Ultraviolet Absorption Spectrum of a Criegee Intermediate CH 2 OO
journal, November 2013

  • Sheps, Leonid
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 24
  • DOI: 10.1021/jz402191w

UV Photodissociation Dynamics of the CH 3 CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products
journal, July 2015

  • Li, Hongwei; Fang, Yi; Kidwell, Nathanael M.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 30
  • DOI: 10.1021/acs.jpca.5b05352

Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis
journal, December 2018

  • Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 149, Issue 24
  • DOI: 10.1063/1.5064716

A Simple and Efficient Method for Simulating the Electronic Absorption Spectra of Criegee Intermediates: Benchmarking on CH 2 OO and CH 3 CHOO
journal, May 2021

  • McCoy, Julia C.; Marchetti, Barbara; Thodika, Mushir
  • The Journal of Physical Chemistry A, Vol. 125, Issue 19
  • DOI: 10.1021/acs.jpca.1c01074

Analytical Derivative Coupling for Multistate CASPT2 Theory
journal, May 2017

  • Park, Jae Woo; Shiozaki, Toru
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 6
  • DOI: 10.1021/acs.jctc.7b00018

UV absorption spectrum and photodissociation dynamics of CH2OO following excitation to the B1 A′ state
journal, July 2021

Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years
journal, January 2014

  • Sindelarova, K.; Granier, C.; Bouarar, I.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 17
  • DOI: 10.5194/acp-14-9317-2014

Correlated quantum treatment of the photodissociation dynamics of formaldehyde oxide CH2OO
journal, January 2022

  • Nikoobakht, Behnam; Köppel, Horst
  • Physical Chemistry Chemical Physics, Vol. 24, Issue 20
  • DOI: 10.1039/D2CP01007K

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

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Multiphoton optical and photoelectron spectroscopy of 4 s –3 d and 5 s –4 d Rydberg complexes of O 2
journal, December 1988

  • Park, Haiyoon; Miller, Paul J.; Chupka, William A.
  • The Journal of Chemical Physics, Vol. 89, Issue 11
  • DOI: 10.1063/1.455340

The on-the-fly surface-hopping program system Newton-X: Application to ab initio simulation of the nonadiabatic photodynamics of benchmark systems
journal, August 2007

  • Barbatti, Mario; Granucci, Giovanni; Persico, Maurizio
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 190, Issue 2-3
  • DOI: 10.1016/j.jphotochem.2006.12.008

Mechanism of Ozonolysis
journal, November 1975

  • Criegee, Rudolf
  • Angewandte Chemie International Edition in English, Vol. 14, Issue 11
  • DOI: 10.1002/anie.197507451

Second‐order perturbation theory with a complete active space self‐consistent field reference function
journal, January 1992

  • Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O.
  • The Journal of Chemical Physics, Vol. 96, Issue 2
  • DOI: 10.1063/1.462209

Absolute UV absorption cross sections of dimethyl substituted Criegee intermediate (CH 3 ) 2 COO
journal, June 2016

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate
journal, April 2020

  • Caravan, Rebecca L.; Vansco, Michael F.; Au, Kendrew
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 18
  • DOI: 10.1073/pnas.1916711117

Electronic‐Relaxation Processes in Acetone
journal, February 1966

  • Borkman, Raymond F.; Kearns, David R.
  • The Journal of Chemical Physics, Vol. 44, Issue 3
  • DOI: 10.1063/1.1726846

Two-dimensional charged particle image inversion using a polar basis function expansion
journal, November 2004

  • Garcia, Gustavo A.; Nahon, Laurent; Powis, Ivan
  • Review of Scientific Instruments, Vol. 75, Issue 11
  • DOI: 10.1063/1.1807578

XSEDE: Accelerating Scientific Discovery
journal, September 2014

  • Towns, John; Cockerill, Timothy; Dahan, Maytal
  • Computing in Science & Engineering, Vol. 16, Issue 5
  • DOI: 10.1109/MCSE.2014.80

Effects of the substituents on the reactivity of carbonyl oxides. A theoretical study on the reaction of substituted carbonyl oxides with water
journal, January 2011

  • Anglada, J. M.; González, J.; Torrent-Sucarrat, M.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 28
  • DOI: 10.1039/c1cp20872a

Surprisingly long lifetime of methacrolein oxide, an isoprene derived Criegee intermediate, under humid conditions
journal, February 2021

Insights into the Ultrafast Dynamics of CH 2 OO and CH 3 CHOO Following Excitation to the Bright 1 ππ* State: The Role of Singlet and Triplet States
journal, November 2021

  • Esposito, Vincent J.; Werba, Olivia; Bush, Sarah A.
  • Photochemistry and Photobiology, Vol. 98, Issue 4
  • DOI: 10.1111/php.13560

Prompt release of O 1 D products upon UV excitation of CH 2 OO Criegee intermediates
journal, July 2017

  • Vansco, Michael F.; Li, Hongwei; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 147, Issue 1
  • DOI: 10.1063/1.4977987

Modeling the Rovibrationally Excited C 2 H 4 OH Radicals from the Photodissociation of 2-Bromoethanol at 193 nm
journal, April 2010

  • Ratliff, B. J.; Womack, C. C.; Tang, X. N.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 14
  • DOI: 10.1021/jp911739a

Unimolecular Decay of Criegee Intermediates to OH Radical Products: Prompt and Thermal Decay Processes
journal, March 2018

The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere
journal, January 2008

  • Johnson, David; Marston, George
  • Chemical Society Reviews, Vol. 37, Issue 4
  • DOI: 10.1039/b704260b

The Molpro quantum chemistry package
journal, April 2020

  • Werner, Hans-Joachim; Knowles, Peter J.; Manby, Frederick R.
  • The Journal of Chemical Physics, Vol. 152, Issue 14
  • DOI: 10.1063/5.0005081

Photodissociation Dynamics of CH 2 OO on Multiple Potential Energy Surfaces: Experiment and Theory
journal, July 2021

  • Esposito, Vincent J.; Liu, Tianlin; Wang, Guanghan
  • The Journal of Physical Chemistry A, Vol. 125, Issue 30
  • DOI: 10.1021/acs.jpca.1c03643

Absolute two-photon absorption and three-photon ionization cross sections for atomic oxygen
journal, July 1986

  • Bamford, Douglas J.; Jusinski, Leonard E.; Bischel, William K.
  • Physical Review A, Vol. 34, Issue 1
  • DOI: 10.1103/PhysRevA.34.185

Dynamics and spectroscopy of CH 2 OO excited electronic states
journal, January 2016

  • Kalinowski, Jaroslaw; Foreman, Elizabeth S.; Kapnas, Kara M.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C6CP00807K

Velocity map imaging of O-atom products from UV photodissociation of the CH2OO Criegee intermediate
journal, June 2015

  • Li, Hongwei; Fang, Yi; Beames, Joseph M.
  • The Journal of Chemical Physics, Vol. 142, Issue 21
  • DOI: 10.1063/1.4921990

Research frontiers in the chemistry of Criegee intermediates and tropospheric ozonolysis
journal, January 2014

  • Taatjes, Craig A.; Shallcross, Dudley E.; Percival, Carl J.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 5
  • DOI: 10.1039/c3cp52842a

Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation
journal, January 2013

  • Percival, Carl J.; Welz, Oliver; Eskola, Arkke J.
  • Faraday Discussions, Vol. 165
  • DOI: 10.1039/c3fd00048f

A direct dynamics study of the exotic photochemistry of the simplest Criegee intermediate, CH2OO
journal, January 2022

  • Antwi, Ernest; Bush, Rachel E.; Marchetti, Barbara
  • Physical Chemistry Chemical Physics, Vol. 24, Issue 27
  • DOI: 10.1039/D2CP01860H

Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production
journal, July 2018

  • Barber, Victoria P.; Pandit, Shubhrangshu; Green, Amy M.
  • Journal of the American Chemical Society, Vol. 140, Issue 34
  • DOI: 10.1021/jacs.8b06010

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates
journal, September 2022

  • Liu, Tianlin; Zou, Meijun; Caracciolo, Adriana
  • The Journal of Physical Chemistry A, Vol. 126, Issue 38
  • DOI: 10.1021/acs.jpca.2c05502

Ion imaging study of IO radical photodissociation: Accurate bond dissociation energy determination
journal, May 2008

Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact
journal, December 2019

UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH 2 OO)
journal, December 2014

  • Dawes, Richard; Jiang, Bin; Guo, Hua
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja510736d

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

The conformational changes accompanying the triplet–singlet electronic excitation of acetaldehyde, CH 3 CHO
journal, July 1985

  • Moule, D. C.; Ng, K. H. K.
  • Canadian Journal of Chemistry, Vol. 63, Issue 7
  • DOI: 10.1139/v85-236

A Modified Multistep Method for the Numerical Integration of Ordinary Differential Equations
journal, January 1965

Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn -CH 3 CHOO through pure rotational transitions
journal, January 2014

  • Nakajima, Masakazu; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 140, Issue 1
  • DOI: 10.1063/1.4861494

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO 2
journal, August 2015

  • Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 35
  • DOI: 10.1073/pnas.1513149112

Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates
journal, January 2017

  • Vereecken, L.; Novelli, A.; Taraborrelli, D.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 47
  • DOI: 10.1039/C7CP05541B

Second-order perturbation theory with a CASSCF reference function
journal, July 1990

  • Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O.
  • The Journal of Physical Chemistry, Vol. 94, Issue 14
  • DOI: 10.1021/j100377a012

Theoretical study of photochemical processes involving singlet excited states of formaldehyde carbonyl oxide in the atmosphere
journal, December 2002

UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH 3 CHOO
journal, January 2014

  • Sheps, Leonid; Scully, Ashley M.; Au, Kendrew
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 48
  • DOI: 10.1039/C4CP04408H

Electron energy-loss spectroscopy of forbidden transitions to valence and Rydberg states of formaldehyde
journal, September 1982

Photodissociation dynamics of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis
journal, November 2021

  • Wang, Guanghan; Liu, Tianlin; Caracciolo, Adriana
  • The Journal of Chemical Physics, Vol. 155, Issue 17
  • DOI: 10.1063/5.0068664

Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO
journal, April 2013

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates
journal, July 2022

  • Karsili, Tolga N. V.; Marchetti, Barbara; Lester, Marsha I.
  • Photochemistry and Photobiology
  • DOI: 10.1111/php.13665

Theoretical studies of atmospheric reaction mechanisms in the troposphere
journal, January 2012

  • Vereecken, Luc; Francisco, Joseph S.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35070j

Double-resonance spectroscopy of transitions between autoionizing levels of atomic oxygen
journal, May 1991

Wave Packet Calculation of Absolute UV Cross Section of Criegee Intermediates
journal, August 2022

Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere
journal, June 2018

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates
journal, November 2020

  • Cox, R. Anthony; Ammann, Markus; Crowley, John N.
  • Atmospheric Chemistry and Physics, Vol. 20, Issue 21
  • DOI: 10.5194/acp-20-13497-2020

Ultrafast dissociation dynamics of acetone: A revisit to the S1 state and 3s Rydberg state
journal, January 1999

  • Zhong, Q.; Poth, L.; Castleman, A. W.
  • The Journal of Chemical Physics, Vol. 110, Issue 1
  • DOI: 10.1063/1.478793
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: