UV absorption spectrum and photodissociation channels of the simplest Criegee intermediate (CH2OO). Dawes, R.; Jiang, B.; and Guo, H. Journal of the American Chemical Society, 12, 2014.
UV absorption spectrum and photodissociation channels of the simplest Criegee intermediate (CH2OO). [pdf]Paper  UV absorption spectrum and photodissociation channels of the simplest Criegee intermediate (CH2OO). [link]Website  abstract   bibtex   
The 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. It is found that a high-level treatment of dynamic electron-correlation is essential to accurately describe these states. We find a significant well on the B-state 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.
@article{
 title = {UV absorption spectrum and photodissociation channels of the simplest Criegee intermediate (CH2OO).},
 type = {article},
 year = {2014},
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 websites = {http://www.ncbi.nlm.nih.gov/pubmed/25470300},
 month = {12},
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 abstract = {The 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. It is found that a high-level treatment of dynamic electron-correlation is essential to accurately describe these states. We find a significant well on the B-state 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.},
 bibtype = {article},
 author = {Dawes, Richard and Jiang, Bin and Guo, Hua},
 journal = {Journal of the American Chemical Society}
}
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