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Search for Stratospheric Bromine Reservoir Species:  Theoretical Study of the Photostability of Mono-, Tri-, and Pentacoordinated Bromine Compounds

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journal contribution
posted on 15.09.2005, 00:00 by Timothy J. Lee, Cesar N. Mejia, Gregory J. O. Beran, Martin Head-Gordon
Previous work has shown that pentacoordinated bromine compounds have their lowest excited electronic states shifted to the blue relative to monocoordinated bromine molecules, and that this shift may be large enough to render them photostable in the lower stratosphere. Our earlier work has also shown that certain pentacoordinated bromine compounds are thermodynamically stable relative to their mono- or tricoordinated isomers, suggesting that if a bromine stratospheric reservoir species exists, it may be a pentacoordinated compound. In this study we have examined the singlet and triplet excited electronic states of several bromine compounds, using time dependent density functional theory, to assess their photostability under stratospheric conditions and in order to elucidate the nature of lowest excited states in mono-, tri-, and pentacoordinated bromine molecules. The triplet states have been included due to the strong spin−orbit mixing in bromine. We have found several pentacoordinated bromine/oxygen compounds that could be photostable in the lower stratosphere, but we have also found that monovalent bromine compounds where the bromine atom is bonded to an atom with no lone-pair p-electrons is far and away the most photostable. Attachment/detachment electron density plots have been useful in ascertaining the nature of the excited electronic states and their likely path to photodissociation.