Bd. 72, Nr.

2
1968 K. H. Diexhage, 11. Kuhn, and F. P. Schifer: Variation of the Fluorescence Decay- Time etc. 329

Discussion
M . Sfockburger: F. P. Schaj'er :
1) H o w high is the power output of the laser emission 1) 1 MW plus.
you obtain from your special Brewster angle cuvette ? 2) Second harmonic light of ruby lasers and neodymium
2) Have you already used successfully other sources of glass lasers give excitation wavelengths of 347 and 532 nm,
excitation than giant-pulse ruby laser emission or flash respectively. Air and surface sparks (Gleitfunken) were also
lamps ? successfully used to excite dye lasers. E 1315

Variation of the Fluorescence Decay Time of a Molecule in Front of a Mirror

By K. H. D R E X H A G E , H. KUHN, and F. P. S C H A F E R

Physikalisch-Chemisches Institut der Universitat Marburg

Presented at the International Conference on Photochemistry, September 6-9, 1967 Miinchen

The out-going wave-front of a radiating oscillator (e.g. a Hertzian dipole) is disturbed by a reflecting
surface. The resulting interference phenomenon affects the radiated power, which thus depends on the
distance between oscillator and mirror. If this concept is applied to the emission of light by molecules,
a dependence of the fluorescence decay time o n the distance between excited molecule and mirror is to
be expected.
This effect has been investigated for the case of monomolecular layers of an europium dibenzoylmethane
complex, which are kept in a definite distance from an evaporated metal surface (gold, silver or alumi-
num) by cadmiumarachidate layers. Exciting with a flash of 366 nm light the intense red fluorescence
(d = 612 nm) of the europium ion is observed. The fluorescence follows an exponential decay law over
at least two decades with a decay time of roughly 1 msec. The expected variation of the decay time with
distance from the mirror is verified by the experiment. The decay time is lengthened or shortened in
close agreement with the above theory, except for small distances, where energy transfer processes
occur.
The mirror affects only the radiating process, while the probabilities for non-radiating desactivation
processes remain unaltered. Thus the quantum yield of fluorescence of the emitting state can be deter-
mined, which is an otherwise hardly accessible quantity.

Discussion
H. Kallnzann :
These very interesting experiments show that the radiative
lifetime of an excited molecule is not a constant, fixed
property of this molecule as one likes to conclude from thc
fact that it is determined by its wavefunction. Here it is
shown that this lifetime depends on the surrounding radia-
tion field. One could describe this in a somewhat primitive
way by saying that the shortening of the lifetime is due to
an enhanced emission and the lengthening to an absorption
from its own emitted radiation field, which comes about
because of the reflection of the emitted radiation by the
mirror. Such a description may be somewhat awkward when
one considers that the emitted wavelength is not strongly
or not at all absorbed by the molecule because of the shift
between the absorption and fluorescence spectra. It is thus
more appropriate to look upon this phenomenon from the
viewpoint of Dirac's radiation theory in which the emission
probability comes about by the coupling of the oscillator
with its own radiation field. Since the mirror in these ex-
periments changes the distribution of the radiation field,
also the coupling between the radiation and the emitting
dipole is changed.
K. H . Drexhage :
I n my talk I have only considered the classical inter-
pretation of the investigated phenomenon, since this is
sufficient for a quantitative evaluation of the experiments.
As you correctly remarked, a quantum-mechanical de-
scription would have to include the coupling between the
oscillator and its own radiation field. Otherwise the influence
of the mirror on the lifetime cannot be understood.
E. W. Schlag :
H o w did you eliminate effects due to trapping of fluores-
cence by neighboring molecules, and hence an additional
lifetime shift. Particularly in the solid state one might expect
strong emission from low lying vibronic levels which are
the ones that usually overlap the absorption spectrum.
K. H . Drexbage :
In the case of the investigated europium complex the
absorption at the fluorescence wavelength (A = 612 nm) is
extremely small. The oscillator strength is only f =
I n addition a lifetime shift caused by reabsorption would
be independent of the distance between fluorescing layer
and mirror. E 1317