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NEGATIVE ION PHOTOELECTRON SPECTRA OF DIHALOCARBENES AND DIHALOMETHYL RADICALS

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/33588

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Title: NEGATIVE ION PHOTOELECTRON SPECTRA OF DIHALOCARBENES AND DIHALOMETHYL RADICALS
Creators: Wren, Scott; Vogelhuber, Kristen M.; Lineberger, W. Carl
Issue Date: 2008
Abstract: Dihalocarbenes of the form CX$_2$ (X = F, Cl, Br, I) are important intermediates in organic reactions, due to the unique chemical properties of their low-lying neutral singlet $^1$A$_1$ and triplet $^3$B$_1$ states that affect their reactivities. Disagreement between experimental and theoretical results for the singlet-triplet splittings in CCl$_2$$^-$, CBr$_2$$^-$, and CI$_2$$^-$ prompted a careful reinvestigation of the photoelectron spectra of these compounds, revealing contamination from HCX$_2$$^-$ species. Contributions from contaminants previously obscuring the dihalocarbene $^3$B$_1$ triplet spectra have been minimized, and photoelectron spectra of isolated HCX$_2$$^-$ compounds were collected to further elucidate the dihalocarbene experimental data. The new CCl$_2$$^-$ 351 nm photoelectron spectra exhibit vibrationally resolved transitions to singlet and triplet electronic states; careful analysis drastically alters the previous identification of the triplet state origin, resulting in substantially improved agreement with high level calculations.
URI: http://hdl.handle.net/1811/33588
Other Identifiers: 2008-RI-13
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