Ultrafast Photochemistry of Bromoform in Solution Probed in the Deep-Uv to Near-Ir Spectral Range

Details Ultrafast Photochemistry of Bromoform in Solution Probed in the Deep-Uv to Near-Ir Spectral Range Ultrafast Photochemistry of Bromoform in Solution Probed in the Deep-Uv to Near-Ir Spectral Range

Jun 2010

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2010mss..confewf05p&link_type=abstract

"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspec

Physics

Electronic (Uv/Vis/Nir)

Scientific paper

The photochemical pathways of bromoform (CHBr_3) in dilute (10 mM) and concentrated (500 mM) acetonitrile and methylcyclohexane solutions following excitation with ultrafast (100 fs) 255-nm laser pulses were investigated. Ultrafast transient absorption spectra manifest the formation of a CHBr_2 radical species within the apparatus response function through its intense deep-UV (˜ 250-nm) absorption band. The formation of iso-bromoform (iso-CHBr_2-Br) occurs within few hundreds of femtoseconds after photoexcitation and do not correlate with the dynamics of CHBr_2 radical. The iso- CHBr_2-Br isomer species decays single exponentially with a 290-ps time constant in acetonitrile. In methylcyclohexane, however, the intense absorption of the isomer in the visible spectral range dominates the transient spectra up to the longest investigated time delays of 1.2 ns. Ab initio and DFT calculations in conjunction with continuum solvation models strongly suggest that acetonitrile opens a pathway for the iso-CHBr_2-Br to CHBr_3 isomerization through a polar, cyclic transition state. This channel is not thermodynamically feasible in the non-polar solvent.

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