UV Photodissociation Dynamics of the CH3CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products

Li, Hongwei; Fang, Yi; Kidwell, Nathanael M.; Beames, Joseph M.; Lester, Marsha I.

doi:10.1021/acs.jpca.5b05352

UV Photodissociation Dynamics of the CH₃CHOO Criegee Intermediate: Action Spectroscopy and Velocity Map Imaging of O-Atom Products

Journal Article · Mon Jul 20 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b05352· OSTI ID:1598535

Li, Hongwei ^[1]; Fang, Yi ^[2]; Kidwell, Nathanael M. ^[2]; Beames, Joseph M. ^[2]; Lester, Marsha I. ^[2]

Univ. of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania
Univ. of Pennsylvania, Philadelphia, PA (United States)

We report that UV excitation of jet-cooled CH₃CHOO on the B¹A'–X¹A' transition results in dissociation to two spin-allowed product channels: CH₃CHO X¹A' + O ¹D and CH₃CHO a³A" + O ³P. The O ¹D and O ³P products are detected using 2 + 1 REMPI at 205 and 226 nm, respectively, for action spectroscopy and velocity map imaging studies. The O ¹D action spectrum closely follows the previously reported UV absorption spectrum for jet-cooled CH₃CHOO [Beames et al. J. Chem. Phys. 2013, 138, 244307]. Velocity map images of the O ¹D products following excitation of CH₃CHOO at 305, 320, and 350 nm exhibit anisotropic angular distributions indicative of rapid (ps) dissociation, along with broad and unstructured total kinetic energy (TKER) distributions that reflect the internal energy distribution of the CH₃CHO X¹A' coproducts. The O ³P action spectrum turns on near the peak of the UV absorption spectrum (ca. 324 nm) and extends to higher energy with steadily increasing O ³P yield. Excitation of CH₃CHOO at 305 nm, attributed to absorption of the more stable syn-conformer, also results in an anisotropic angular distribution of O ³P products arising from rapid (ps) dissociation, but a narrower TKER distribution since less energy is available to the CH₃CHO a³A" + O ³P products. The threshold for the higher energy CH₃CHO a³A" + O ³P product channel is determined to be ca. 88.4 kcal mol^–1 from the termination of the TKER distribution and the onset of the O ³P action spectrum. This threshold is combined with the singlet-triplet spacings of O atoms and acetaldehyde to establish the dissociation energy for syn-CH₃HOO X¹A' to the lowest spin-allowed product channel, CH₃CHO X¹A' + O ¹D, of ≤55.9 ± 0.4 kcal mol^–1. Lastly, a harmonic normal-mode analysis is utilized to identify the vibrational modes of CH₃CHO likely to be excited upon dissociation into the two product channels.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-87ER13792

OSTI ID:: 1598535

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 30 Vol. 119; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

A CCSD (T) investigation of carbonyl oxide and dioxirane. Equilibrium geometries, dipole moments, infrared spectra, heats of formation and isomerization energies Cremer, Dieter; Gauss, Jürgen; Kraka, Elfi Chemical Physics Letters, Vol. 209, Issue 5-6 https://doi.org/10.1016/0009-2614(93)80131-8	journal	July 1993
Fast beam studies of I2− and I2−·Ar photodissociation Hoops, Alexandra A.; Gascooke, Jason R.; Faulhaber, Ann Elise Chemical Physics Letters, Vol. 374, Issue 3-4 https://doi.org/10.1016/S0009-2614(03)00708-5	journal	June 2003
Heats of formation of the Criegee formaldehyde oxide and dioxirane Nguyen, Minh Tho; Nguyen, Thanh Lam; Ngan, Vu Thi Chemical Physics Letters, Vol. 448, Issue 4-6 https://doi.org/10.1016/j.cplett.2007.10.033	journal	November 2007
Ion imaging study of IO radical photodissociation: Accurate bond dissociation energy determination Dooley, Kristin S.; Geidosch, Justine N.; North, Simon W. Chemical Physics Letters, Vol. 457, Issue 4-6 https://doi.org/10.1016/j.cplett.2008.04.009	journal	May 2008
Ion imaging studies of the photodissociation dynamics of CH2I2 at 248nm Lehman, Julia H.; Li, Hongwei; Lester, Marsha I. Chemical Physics Letters, Vol. 590 https://doi.org/10.1016/j.cplett.2013.10.029	journal	December 2013
Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH ₂ OO Beames, Joseph M.; Liu, Fang; Lu, Lu Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja310603j	journal	December 2012
UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH ₂ OO) Dawes, Richard; Jiang, Bin; Guo, Hua Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja510736d	journal	December 2014
Unimolecular Isomerizations and Oxygen Atom Loss in Formaldehyde and Acetaldehyde Carbonyl Oxides. A Theoretical Investigation Anglada, Josep M.; Bofill, Josep M.; Olivella, Santiago Journal of the American Chemical Society, Vol. 118, Issue 19 https://doi.org/10.1021/ja953858a	journal	January 1996
Computational Studies of the Isomerization and Hydration Reactions of Acetaldehyde Oxide and Methyl Vinyl Carbonyl Oxide Kuwata, Keith T.; Hermes, Matthew R.; Carlson, Matthew J. The Journal of Physical Chemistry A, Vol. 114, Issue 34 https://doi.org/10.1021/jp105358v	journal	September 2010
UV Spectroscopic Characterization of Dimethyl- and Ethyl-Substituted Carbonyl Oxides Liu, Fang; Beames, Joseph M.; Green, Amy M. The Journal of Physical Chemistry A, Vol. 118, Issue 12 https://doi.org/10.1021/jp412726z	journal	March 2014
Modeling the Rovibrationally Excited C ₂ H ₄ OH Radicals from the Photodissociation of 2-Bromoethanol at 193 nm Ratliff, B. J.; Womack, C. C.; Tang, X. N. The Journal of Physical Chemistry A, Vol. 114, Issue 14 https://doi.org/10.1021/jp911739a	journal	April 2010
Infrared identification of the Criegee intermediates syn- and anti-CH3CHOO, and their distinct conformation-dependent reactivity Lin, Hui-Yu; Huang, Yu-Hsuan; Wang, Xiaohong Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8012	journal	May 2015
UV absorption probing of the conformer-dependent reactivity of a Criegee intermediate CH ₃ CHOO Sheps, Leonid; Scully, Ashley M.; Au, Kendrew Phys. Chem. Chem. Phys., Vol. 16, Issue 48 https://doi.org/10.1039/C4CP04408H	journal	January 2014
The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere Johnson, David; Marston, George Chemical Society Reviews, Vol. 37, Issue 4 https://doi.org/10.1039/b704260b	journal	January 2008
Theoretical studies of atmospheric reaction mechanisms in the troposphere Vereecken, Luc; Francisco, Joseph S. Chemical Society Reviews, Vol. 41, Issue 19 https://doi.org/10.1039/c2cs35070j	journal	January 2012
The conformational structures and dipole moments of ethyl sulfide in the gas phase Plusquellic, D. F.; Suenram, R. D.; Maté, B. The Journal of Chemical Physics, Vol. 115, Issue 7 https://doi.org/10.1063/1.1385527	journal	August 2001
Reconstruction of Abel-transformable images: The Gaussian basis-set expansion Abel transform method Dribinski, Vladimir; Ossadtchi, Alexei; Mandelshtam, Vladimir A. Review of Scientific Instruments, Vol. 73, Issue 7 https://doi.org/10.1063/1.1482156	journal	July 2002
Multiphoton optical and photoelectron spectroscopy of 4 s –3 d and 5 s –4 d Rydberg complexes of O ₂ Park, Haiyoon; Miller, Paul J.; Chupka, William A. The Journal of Chemical Physics, Vol. 89, Issue 11 https://doi.org/10.1063/1.455340	journal	December 1988
Identification of the ns σ and nd λ Rydberg states of O ₂ for n =3–5 Yokelson, R. J.; Lipert, R. J.; Chupka, W. A. The Journal of Chemical Physics, Vol. 97, Issue 9 https://doi.org/10.1063/1.463724	journal	November 1992
The T ₁ ( n π*)← S ₀ laser induced phosphorescence excitation spectrum of acetaldehyde in a supersonic free jet: Torsion and wagging potentials in the lowest triplet state Liu, H.; Lim, E. C.; Muñoz‐Caro, C. The Journal of Chemical Physics, Vol. 105, Issue 7 https://doi.org/10.1063/1.472120	journal	August 1996
Photoelectron and photofragment velocity map imaging of state-selected molecular oxygen dissociation/ionization dynamics Parker, D. H.; Eppink, A. T. J. B. The Journal of Chemical Physics, Vol. 107, Issue 7 https://doi.org/10.1063/1.474624	journal	August 1997
Angular distributions for photodissociation of O2 in the Herzberg continuum Buijsse, B.; van der Zande, W. J.; Eppink, A. T. J. B. The Journal of Chemical Physics, Vol. 108, Issue 17 https://doi.org/10.1063/1.476141	journal	May 1998
UV spectroscopic characterization of an alkyl substituted Criegee intermediate CH ₃ CHOO Beames, Joseph M.; Liu, Fang; Lu, Lu The Journal of Chemical Physics, Vol. 138, Issue 24 https://doi.org/10.1063/1.4810865	journal	June 2013
Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH ₂ OO Lehman, Julia H.; Li, Hongwei; Beames, Joseph M. The Journal of Chemical Physics, Vol. 139, Issue 14 https://doi.org/10.1063/1.4824655	journal	October 2013
Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn -CH ₃ CHOO through pure rotational transitions Nakajima, Masakazu; Endo, Yasuki The Journal of Chemical Physics, Vol. 140, Issue 1 https://doi.org/10.1063/1.4861494	journal	January 2014
UV absorption spectrum of the C2 Criegee intermediate CH ₃ CHOO Smith, Mica C.; Ting, Wei-Lun; Chang, Chun-Hung The Journal of Chemical Physics, Vol. 141, Issue 7 https://doi.org/10.1063/1.4892582	journal	August 2014
Quantum dynamical investigation of the simplest Criegee intermediate CH ₂ OO and its O–O photodissociation channels Samanta, Kousik; Beames, Joseph M.; Lester, Marsha I. The Journal of Chemical Physics, Vol. 141, Issue 13 https://doi.org/10.1063/1.4894746	journal	October 2014
A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C. The Journal of Chemical Physics, Vol. 142, Issue 12 https://doi.org/10.1063/1.4914987	journal	March 2015
Velocity map imaging of O-atom products from UV photodissociation of the CH2OO Criegee intermediate Li, Hongwei; Fang, Yi; Beames, Joseph M. The Journal of Chemical Physics, Vol. 142, Issue 21 https://doi.org/10.1063/1.4921990	journal	June 2015
Non-Adiabatic Crossing of Energy Levels Zener, C. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 137, Issue 833 https://doi.org/10.1098/rspa.1932.0165	journal	September 1932
Direct Measurements of Conformer-Dependent Reactivity of the Criegee Intermediate CH3CHOO Taatjes, C. A.; Welz, O.; Eskola, A. J. Science, Vol. 340, Issue 6129 https://doi.org/10.1126/science.1234689	journal	April 2013
Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates to OH radical products Liu, F.; Beames, J. M.; Petit, A. S. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1257158	journal	September 2014
The conformational changes accompanying the triplet–singlet electronic excitation of acetaldehyde, CH ₃ CHO Moule, D. C.; Ng, K. H. K. Canadian Journal of Chemistry, Vol. 63, Issue 7 https://doi.org/10.1139/v85-236	journal	July 1985
The electronic spectra of acetaldehyde- h ₄ and - d ₄ Yakovlev, N. N.; Godunov, I. A. Canadian Journal of Chemistry, Vol. 70, Issue 3 https://doi.org/10.1139/v92-125	journal	March 1992

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Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products Kidwell, Nathanael M.; Li, Hongwei; Wang, Xiaohong Nature Chemistry, Vol. 8, Issue 5 https://doi.org/10.1038/nchem.2488	journal	April 2016
Communication: Thermal unimolecular decomposition of syn-CH ₃ CHOO: A kinetic study Nguyen, Thanh Lam; McCaslin, Laura; McCarthy, Michael C. The Journal of Chemical Physics, Vol. 145, Issue 13 https://doi.org/10.1063/1.4964393	journal	October 2016
Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I. The Journal of Chemical Physics, Vol. 149, Issue 24 https://doi.org/10.1063/1.5064716	journal	December 2018
Catalytic effect of water, water dimer, water trimer, HCOOH, H ₂ SO ₄ , CH ₃ CH ₂ COOH and HN(NO ₂ ) ₂ on the isomerisation of HN(NO ₂ ) ₂ to O ₂ NNN(O)OH: a mechanism study Wang, Rui; Jia, Zi-long; An, Yi-ming Molecular Physics, Vol. 115, Issue 13 https://doi.org/10.1080/00268976.2017.1301589	journal	March 2017
Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact Stephenson, Thomas A.; Lester, Marsha I. International Reviews in Physical Chemistry, Vol. 39, Issue 1 https://doi.org/10.1080/0144235x.2020.1688530	journal	December 2019
Catalytic effect of water, water dimer, HCOOH and H ₂ SO ₄ on the isomerisation of HON(O)NNO ₂ to ON(OH)NNO ₂ : a mechanism study Zhang, Tian-lei; Lan, Xin-guang; Wen, Ming-jie Molecular Simulation, Vol. 44, Issue 18 https://doi.org/10.1080/08927022.2018.1518578	journal	September 2018

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