Picosecond time-resolved resonance Raman observation of the iso-CH2Cl-I and iso-CH2I-Cl photoproducts from the "photoisomerization" reactions of CH2ICl in the solution phase

We report a preliminary picosecond Stokes time-resolved resonance Raman inv estigation of the initial formation and subsequent decay of the photoproduc t produced following 267 nm excitation of CH2ClI in acetonitrile solution. Density-functional theory computations were done for several probable photo product species. Comparison of these computational results and results from a recent femtosecond transient absorption study to our present picosecond resonance Raman spectra indicate that the iso-CH2Cl-I species is mainly pro duced and associated with the similar to 460 nm transient absorption band. The iso-CH2Cl-I species appears to decay and form appreciable amounts of th e more stable iso-CH2I-Cl species that is associated with a similar to 370 nm transient absorption band after a few hundred ps. (C) 2001 American Inst itute of Physics.