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Article
UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH2OO)
Journal of the American Chemical Society
  • Richard Dawes, Missouri University of Science and Technology
  • Bin Jiang
  • Hua Guo
Abstract
The lowest-lying singlet states of the simplest Criegee intermediate (CH2OO) have been characterized along the O-O dissociation coordinate using explicitly correlated MRCI-F12 electronic structure theory and large active spaces. It is found that a high-level treatment of dynamic electron-correlation is essential to accurately describe these states. a significant well on the B-state is identified at the MRCI-F12 level with an equilibrium structure that differs substantially from that of the ground X-state. This well is presumably responsible for the apparent vibrational structure in some experimental UV absorption spectra, analogous to the structured Huggins band of the iso-electronic ozone. the B-state potential in the Franck-Condon region is sufficiently accurate that an absorption spectrum calculated with a one-dimensional model agrees remarkably well with experiment.
Department(s)
Chemistry
Research Center/Lab(s)
Center for High Performance Computing Research
Keywords and Phrases
  • Absorption spectra,
  • Electromagnetic wave absorption,
  • Electronic structure,
  • Light absorption,
  • Photodissociation,
  • Criegee intermediates,
  • Electronic structure theory,
  • Equilibrium structures,
  • High-level treatment,
  • Lowest-lying singlet state,
  • One-dimensional model,
  • UV absorption spectrum,
  • Vibrational structures,
  • Absorption spectroscopy,
  • formaldehyde,
  • alkene,
  • ozone,
  • Article,
  • calculation,
  • dissociation,
  • experimental study,
  • geometry,
  • simplest criegee intermediate,
  • ultraviolet spectroscopy,
  • chemistry,
  • photochemistry,
  • ultraviolet spectrophotometry,
  • Alkenes,
  • Ozone,
  • Photochemical Processes,
  • Spectrophotometry, Ultraviolet
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2015 American Chemical Society (ACS), All rights reserved.
Publication Date
1-1-2015
Citation Information
Richard Dawes, Bin Jiang and Hua Guo. "UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH2OO)" Journal of the American Chemical Society Vol. 137 Iss. 1 (2015) p. 50 - 53 ISSN: 0002-7863
Available at: http://works.bepress.com/richard_dawes/44/