A molecular reference for PSP showed an unexpected temperature dependence.
At atmospheric pressure the slope of the temperature dependence was similar
to - 0.2%/degrees C at all temperatures. However, at vacuum the temperatur
e dependence had a negative slope at lower temperature (similar to 10 degre
es C) but a positive slope at higher temperature (similar to 40 degrees C).
We attribute this to delayed fluorescence. At higher temperature in the ab
sence of oxygen, the excited singlet state can be thermally repopulated fro
m the triplet state. This results in an increase in the apparent fluorescen
ce as temperature rises. The fluorescence decay at vacuum and 50 degrees C
is composed of two parts: a short (similar to 10 ns) decay from the prompt
fluorescence and a longer-lived (similar to 40 ms) decay from the delayed f
luorescence, which reflects the triplet decay time. Delayed fluorescence is
quenched at 2% atmospheric pressure, so it should not be a problem in wind
-tunnel research, although it can cause confusion in calibration runs at va
cuum. (C) 1999 Elsevier Science B.V. All rights reserved.