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5080 J. Phys. Chem. 1988, 92, 5080-5082
1 I lifetime is determined by the triplet character of the excited mixed
singlet-triplet states. It is believed that the nonradiative rate of
the Tl-So intersystem crossing steeply depends on the vibrational
energy. On the basis of this expectation, we state that the PE
spectrum may be exponentially reduced at E, 2000 cm-. As
ENERGY RESOLVED PHOSPHORESCENCE Tomer et al. used a delayed gating of more than 1 ,us, a triplet
ier3728 i
: nonradiative lifetime of 0.5 hs can result in more than an order
of magnitude reduction of any transition in this energy range. We
also note that the implication of the expected triplet lifetime
reduction also pertains to the identification of hot bands and the
existence and location of the second triplet electronic
I1 1 I I
3700 3900 4100 4300 45~0 In the case of pyrazine, lifetime measurement cannot help in
WAVELENGTH Ci) identification of the triplet from the singlet hot bands except if
Figure 1. Energy-resolved phosphorescence of pyrazine. Pyrazine was a biexponential decay is observed (as indeed measured by Tomer
excited at the Q branch of its lowest triplet state (Aex zz 3728 A) in a et al.) as the lifetime of the singlet is determined by its triplet
pulsed
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