We have observed quantum beats in the reversible intersystem crossing of simple a-dicarbonyls, and we have analyzed them to obtain information concerning the density of interacting states and the average intramolecular coupling energy. We have analyzed most of the biacetyl quantum beats using a method based on the properties of random matrices which is described elsewhere and we present the results here. We also present an analysis based on perturbation theory using the Fourier transforms of the quantum beats which is appropriate for understanding the methylglyoxal quantum beats. The density of vibrationally hot triplet states which interact with excited singlet states that are connected to the ground electronic state via optical excitation (∼22 000 cm -1) is found to increase with the amount of vibrational excitation in the accessible singlet state at roughly the same rate as the overall density of triplet vibrational stress increases. We find satisfactory agreement between the density obtained from the quantum beats and that calculated using well known analytical formulas and direct state counting. The density of interacting states increases with the rotational quantum number of the initially excited singlet rovibronic state. The average value of the magnitude of the spin-orbit interaction is 1-10 MHz independent of the amount of vibrational-rotational excitation present. Radiationless transitions in these highly excited molecules are evidently not subject to any overriding selection rules other than spatial symmetry, and conservation of total energy, total angular momentum, and nuclear spin. The biacetyl quantum beats are collisionally quenched with helium at the same rate as the overall fluorescence. The cross section for this process is roughly 300 ±200 Å2.
|Original language||English (US)|
|Number of pages||11|
|Journal||The Journal of Chemical Physics|
|State||Published - 1980|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry