Dynamics of excimer formation and decay in supercritical krypton.

New infrared absorbing species are identified in the pulse radiolysis of supercritical Kr at high pressures. The species are believed to be excimers. Their formation and decay rates have been time resolved using the Laser Electron Accelerator Facility. An initial species, formed in less than 1 ns, absorbs at several wavelengths between 790 and 1300 nm; The decay of this species is initially fast, followed by a slower component; the decay rate increases with pressure. As this initial species decays a second excimer is formed absorbing at 830, 890, and 990 nm. The growth and decay rates of this excimer are also pressure dependent. A third excimer, absorbing between 1000 and 1200 nm grows at a rate similar to that of the decay of the second species. The decay rate of the third species is also pressure dependent; the lifetime increases from 9.4 ns at 109 bar to 49 ns at 15 bar. A kinetic mechanism is proposed that satisfactorily reproduces the experimental results. The first species is identified as a higher energy gerade triplet state excimer and the second as the singlet gerade state. [ABSTRACT FROM AUTHOR]