Hydrogen abstraction dynamics in solution studied by picosecond infrared spectroscopy

Vibrationally quantum-state-specific dynamics of the reactions of CN radicals with organic molecules in solution

“…Thus, several previous studies of reactions in solution have focussed on rates of appearance of ground-state reaction products and the formation of complexes. 7,8,9,10,11,12,13 Nonetheless, well known and the anharmonicities of the vibrational modes enable the spectral signatures of vibrationally excited products to be resolved. 15,16 In order to unravel the influence of the solvent on the reaction it is useful to compare our studies in solution with those of the well-characterized solvent-free dynamics of CN + RH reactions in the gas phase.…”

Photoisomerization and Photoinduced Reactions in Liquid CCl4 and CHCl3

“…For example, Hochstrasser and co-workers 13 and Crim and coworkers 14 used ultrafast transient infra-red (IR) absorption spectroscopy to follow the time dependence of production of HCl from reactions of Cl atoms with alkanes. Crim and coworkers [14][15][16] also used a chargetransfer band in the ultraviolet (UV) region, previously assigned to Cl-solvent complexes, 17,18 to follow the reaction kinetics on picosecond to nanosecond timescales, and applied this approach to reactions of Cl atoms with alkanes, alcohols and chloroalkanes.…”

Vibrationally Quantum-State–Specific Reaction Dynamics of H Atom Abstraction by CN Radical in Solution

“…This prospect was recognized by Hochstrasser and co-workers (10,11), who employed transient IR absorption to examine the products of reactions of Cl atoms or CN radicals with organic 3 solvents. These pioneering experiments provided evidence that ~20% of the DCN products of the CN reaction with CDCl 3 solvent are formed with one quantum of vibrational excitation in the C-D stretching mode.…”