High-resolution discrete absorption spectrum of alpha-methallyl free radical in the vapor phase.

The alpha-methallyl free radical is formed in the flash photolysis of 3-methylbut-1-ene, and cis-pent-2-ene in the vapor phase, and then subsequent reactions have been investigated by kinetic spectroscopy and gas-liquid chromatography. The photolysis flash was of short duration and it was possible to follow the kinetics of the radicals' decay, which occurred predominantly by bimolecular recombination. The measured rate constant for the alpha-methallyl recombination was (3.5+/-0.3) x 10(10) mol(-1) ls(-1) at 295+/-2K. The absolute extinction coefficients of the alpha-methallyl radical are calculated from the optical densities of the absorption bands. Detailed analysis of related absorption bands and lifetime measurements in the original alpha-methallyl high-resolution discrete absorption spectrum image were also carried out by image processing techniques.

Triplet-triplet energy transfer from naphthalene to biacetyl in the vapor phase.

In principle the optical energy absorbed by a complex molecule raises that molecule to one of its excited states, and afterwards this excitation energy decays through the different relaxation channels. Initially, electronically excited naphthalene emits photons in the phosphorescence band of naphthalene and these emitted photons are absorbed by the acceptor molecule biacetyl, then excited biacetyl phosphoresces. In this investigation, sensitized phosphorescence decay times in different conditions were measured for naphthalene-biacetyl system in the vapor phase. The ultraviolet-visible spectrum of biacetyl vapor at room temperature conditions was broad and structureless.