Abstract
Ultrafast broadband transient absorption spectra measured from the deep- ultraviolet to the near-infrared region following single-photon excitation of bromoiodomethane in acetonitrile at different wavelengths manifest chromophore - selective structural rearrangement and carbon-halogen bond dissociation in solution.
Highlights
The control over photochemistry is possible, if one can manipulate the superposition of molecular vibrational or electronic states created by ultrafast laser excitation, the molecular chemical design, and the environment
Previous gas-phase molecular-beam studies of CH2BrI demonstrated that the A-band excitation favors C–I bond cleavage and the C–Br bond cleavage predominates upon excitation into the B-band, [1]
Chromophore-selective photochemistry of CH2BrI in solution is addressed in this work using the ultrafast transient absorption method that exploits broadband probing, including the deep-UV/UV range, which is of superb advantage for the detection of small reaction intermediate and radical species
Summary
The control over photochemistry is possible, if one can manipulate the superposition of molecular vibrational or electronic states created by ultrafast laser excitation, the molecular chemical design, and the environment. The UV absorption spectrum of CH2BrI exhibits two A- and B- bands centered at 266 and 214 nm, dominated by the n(I) → σ*(C–I) and n(Br) → σ*(C–Br) transitions, respectively. Chromophore-selective photochemistry of CH2BrI in solution is addressed in this work using the ultrafast transient absorption method that exploits broadband probing, including the deep-UV/UV range, which is of superb advantage for the detection of small reaction intermediate and radical species.
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