https://doi.org/10.1007/s100530050363
Vibronic state specific predissociation rates from excited electronic states
Max-Planck-Institut für Quantenoptik, 85748 Garching bei
München, Germany
Received:
13
November
1998
Published online: 15 September 1999
It is shown that predissociation can be perceived as a primary process
due to the continuum part of a Morse oscillator potential. In the
model proposed here internal conversion to the ground state is thus not
necessarily the primary process of a consecutive dissociation
but may be a simultaneous decay.
As a consequence, dissociation rates should
show strong variations from specific (ro-) vibrational
states of the first excited electronic states that are similar to those
known from “pure” internal conversion rates. This behaviour is
demonstrated by calculating predissociation rates for the
process. Especially the out-of-plane
modes seem to play an extraordinary role in the excess energy
behaviour of the predissociation rate. At lower excess energies, rates
from single vibronic levels with out-of-plane mode characteristics
may show an increase by several orders of magnitude.
PACS: 33.50.-j – Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion) / 33.80.Gj – Diffuse spectra; predissociation, photodissociation
© EDP Sciences, Società Italiana di Fisica, Springer-Verlag, 1999
