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Communications: Photoinitiated bond dissociation of bromoiodomethane in solution: Comparison of one-photon and two-photon excitations and the formation of iso- and iso-
See supplementary material at http://dx.doi.org/10.1063/1.3374680
for figures illustrating the solvent signal corresponding to Fig. 2
, the rise of the two-photon spectrum at 380 nm near the peak, the effect of the smoothing function used for the 266 nm excitation data in Fig. 3
, the decay of CH2Br–I in acetonitrile, methanol, and 1-butanol, and the absorption spectrum of IBr as a function of solvent.[Supplementary Material]
24.M. B. Robin, Higher Excited States of Polyatomic Molecules (Academic, New York, 1974), Vol. 1;
24.M. B. Robin, Higher Excited States of Polyatomic Molecules (Academic, New York, 1975), Vol. 2.
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Broadband UV-visible femtosecond transient absorption spectroscopy was used to monitor the excited state photochemistry of following one-photon excitation at 266 or 271 nm and two-photon excitation at 395 or 405 nm in 2-butanol. The results for one-photon excitation agree with earlier studies in acetonitrile, showing clear formation of iso- following cleavage of the C–I bond. In contrast, two-photon excitation at 395 nm results in the appearance of a blueshifted photoproduct absorption band assigned to formation of iso- following cleavage of the C–Br bond. The results are discussed in the context of prior experimental and theoretical work and the prospects for optical control of bond cleavage.
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