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J. CHEM. SOC. FARADAY TRANS., 1993, 89(23), 4185-4191 4185

Photophysical Properties of Laser Dyes : Picosecond Laser Flash

Photolysis Studies of Rhodamine 6G, Rhodamine B and Rhodamine
101
Paul C. Beaumont,* David G. Johnson and Barry J. Parsons
Multidisciplinary Research and Innovation Centre, Faculty of Science, Health and Medical Studies,
North East Wales Institute, Deeside, Clwyd, Wales, UK CH5 4BR
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The UV-VIS absorptive and emissive properties of three laser dyes, viz. Rhodamine 6G, Rhodamine B and
Rhodamine 101, have been studied in ethanolic and methanolic solutions. Time-resolved methods were used to
study the decay of the first excited singlet state of each dye. The absorptive properties of the lowest excited
singlet states of Rhodamine 6G, Rhodamine B and Rhodamine 101 were generated using picosecond laser
pulses. Values for the molar absorption coefficient for the S, t S, absorption process were measured, for each
dye, by both comparative and complete-depletion methods. Values for the S, t S, absorption process, in
ethanol, were found to be 3.7 x lo4 (452 nm), 4.4 x lo4 (428 nm) and 4.3 x lo4 (430 nm) dm3 mol-' cm-' for
Rhodamine 101, Rhodamine 6G and Rhodamine 6 respectively with the corresponding values for the S, t S,
absorption process being measured as 7.7 x lo4 (576 nm), 6.4 x lo4 (532 nm) and 3.8 x lo4 (566 nm) dm3 mol-'
cm-' . These results are compared and contrasted with available literature values.

Lasing action, in dye lasers, involves a radiative transition
from the lowest excited singlet state to a vibrational level of
the ground state. The theoretical and practical aspects of the
operation of dye lasers has been reviewed.' Shortly after exci-
tation, the molecules of dye will be located at the lower vibra-
tional levels of the first excited singlet state (Sl). For dyes
such as Rhodamine 6G and Rhodamine B, these relaxation
times have been measured as being in the range 0.5-1.0 P S . ~
We can now consider the presence of two distinct popu-
lations uiz. So and S1. It would clearly be disadvantageous for
the population of S, to absorb a further photon from the
pump beam and, thereby, be excited to some higher energy
level (S").Not only would the absorption process S, t S, be
wasteful of input energy but (and this would also apply as a
result of an S, t So transition) the energy released as heat, in
the subsequent relaxation back to S,, may lead to thermal
degradation effects in solution.
Fluorescence and stimulated emission occur from the
lowest vibrational level of S, to one of the various
rotational-vibrational energy levels of So in accordance with
the Franck-Condon principle. The stimulated emission cross-
,may be calculated from the following expression :'
section, CT,
A4E(1)
CTe =-
8cn2nz
where E(A) is the fluorescence line shape function normalised
such that:
r E ( A ) dA = 4jF
n is the refractive index of the solvent, c is the speed of light
in vucuo, and z is the fluorescence lifetime of the dye. For an
eflticient laser dye the fluorescence quantum yield, @jF x 1.
The gain coefficient of a dye laser at a given wavelength,
&I ),
depends upon a number of parameters:
s(4 = %W,- ~ g ( W -0 % ( W 1 - m c ,
(3)
where a,(1) is the stimulated emission cross-section at A, ~ ~ ( 1 )filtration system. Ground-state absorption spectra were mea-
is the ground-state absorption cross-section at A, CT&) is the
absorption cross-section of the lowest excited singlet state at
A, a@) is the absorption cross-section of the lowest excited
triplet state at 1 and C,, C, and C , are the molecular popu-
lation densities (molecules cm-3) of the first excited singlet,
the ground state and the first excited triplet state respectively.
For most laser dyes, the quantum yield of intersystem cross-
ing is small and the final term in eqn. (3) may be ignored.
Laser gain at any wavelength will be compromised if either
the ground state or the lowest excited singlet state absorb the
emitted light of that wavelength.
In spite of the frequent use of Rhodamine 6G as a dye laser
material, there have been relatively few published determi-
nations of the absorptive properties of the lowest excited
singlet state particularly in the region where lasing
O C C U ~ S . ~ Published
-~~ data for Rhodamine B are rareg and
the authors know of no such information for Rhodamine 101.
The principal difficulty in such measurements has been that
upon excitation of these materials, into the singlet manifold,
an intense burst of fluorescence is observed which may
'blind' the detector and, thereby, render quantitative obser-
vations of absorption processes almost impossible. The col-
linear geometry, used throughout this study, coupled with the
location of the detector at some distance from the sample cell,
has proved useful in reducing complications, due to prompt
fluorescence, often encountered when using right angle
geometry.
It is clear that a thorough knowledge of a variety of
parameters is important when predicting those dyes which
would be efficient lasing materials. Such parameters include
fluorescence quantum efficiency, fluorescence lifetime,
ground-state absorption spectra and excited singlet-singlet
absorption spectra. In this manuscript we concentrate on
examining such properties for three laser dyes viz. Rho-
damine 6G, Rhodamine B and Rhodamine 101.
Experimental
All rhodamine dyes (Lamda-Physik), 2,2'-bipyridine ruthe-
nium(rr) dichloride hexahydrate [G. F. Smith Chemical
Company, Ru(bpy)$'3, absolute alcohol (drawn from labor-
atory stock) and absolute methanol (J. T. Baker) were used as
received. Water was purified by passage through a Millipore
sured with either a Hewlett-Packard 8450A or Hewlett-
Packard 8451A spectrophotometer. Fluorescence emission
spectra were obtained using a Perkin-Elmer MPF-43A spec-
trophotofluorimeter. The spectral response (500-700 nm) of
 View Article Online

4186 J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

the instrument was measured using a combination of the fol- All the experiments were performed at ambient tem-
lowing standards (for which corrected spectra were perature (20 f 2"C), the solutions being in free equilibrium
available): quinine sulfate,' sulforhodamine 101'* and the with the atmosphere.
aluminium chelate of Pontachrome blue-black R.' An exci-
tation wavelength of 530 nm was used in all fluorescence
experiments. Quantum yields of fluorescence were obtained
Results and Discussion
by using solutions optically matched at the excitation wave- Fluorescence Quantum Yields and Fluorescence Lifetimes
length. Dye solutions were prepared such that absorbance
Ground-state absorption spectra for the three rhodamines
values of 0.4 +_ 0.02 were obtained at 530 nm. Each solution studied are shown in Fig. 1. Fluorescence quantum yields
was then diluted by a factor of 10 and emission spectra
were measured relative to Rhodamine 101 in ethanol for
recorded on these diluted samples. The areas under the cor-
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which the quantum efficiency was taken to be unity16 and the

rected emission curves were compared to the area under the
results are presented in Table 1. The fluorescence quantum
corrected emission curve of Rhodamine 101 in ethanol or
yield of Rhodamine 101 in methanol was measured relative
methanol as appropriate. Suprasil quartz fluorescence
to Rhodamine 101 in ethanol and it was found that, after
cuvettes (pathlength 1 cm) were used throughout this study correcting for the change in refractive index,17 the value was
for both fluorescence and picosecond absorption experiments.
unity. Values for Rhodamine 6G and Rhodamine B in meth-
The picosecond absorption apparatus has been described
anol were generated, therefore, by comparison with Rho-
e1~ewhere.l~ The excitation source was the second or third
damine 101 in methanol.
harmonic (532 nm or 355 nm respectively) from a Quantel
YG402 mode-locked N d : YAG laser (pulse width 30 ps).
Pulse and probe beams traverse the cell in a collinear 120 000,
arrangement. Photochemical stability of the dye under study r

was tested by irradiating a dye solution (air saturated, I

ambient temperature, absorbance 532 nm ca. 0.3) with 500 5

-
r

pulses (ca. 2 mJ per pulse) of the laser beam (532 nm) and I

the ground-state absorption spectrum compared to a non- E"

irradiated sample. No change ( > 2%) in ground-state absorp-
tion spectra was observed between irradiated and non- m
L
'I A
irradiated samples. 0 = A
For time-resolved studies the following protocol was used.
Before each experiment the two diode arrays were balanced.
The delay line was set such that excitation occurred 66 & 5 ps r;
C
.- 40 000
after the analysis pulse had interrogated the sample (this c
method allowed for the reticon to see fluorescence produced s
by the excitation pulse). Typically 500 laser pulses (either 532 2
9
Q
nm or 355 nm as appropriate) were averaged in this position
and a series of correction factors, C, were calculated :
0
450 500 5 50 600
(4) wavelength/nm
Fig. 1 Ground-state absorption spectra for ethanolic solutions of
I(N) is the output voltage of the Nth diode; 1 and 2 are used Rhodamine 6G (H),Rhodamine B ( 0 )and Rhodamine 101 (A)
to indicate the two arrays. For the measurement of the differ-
ence absorption spectrum of the excited singlet state, the
sample was excited 66 & 5 ps before the analysis pulse tra- Table 1 Fluorescence lifetimes (r/ns) and emission quantum yields
versed the sample. 500 laser pulses were averaged in each (GF)for Rhodamine 6G,Rhodamine B and Rhodamine 101
experiment and the absorption computed channel by channel
according to : ~~~~~~

Rhodamine 6G ethanol 5.3" 1.34 0.99"

4Sb 0.95'
4.3' 0.W'
3.8d
All the data presented have been treated in this way. Unless Rhodamine B ethanol 2.9" 1.14 0.67"
otherwise stated, all transient spectra were obtained at a time 2.9'~~ 0.65'
delay of 66 & 5 ps after excitation, this delay being sufficient- 0.68'
ly short to ensure negligible lowest excited singlet state loss. Rhodamine 101 ethanol 4.6" 1.17 1.w
Excitation beam energies were attenuated using metal screen 5.38
filters of known transmission at the excitation wavelength.
Singlet excited state lifetimes were measured by a time- Rhodamine 6G methanol 4.9" 1.33 0.89"
4Sb 0.90'
correlated, single-photon counting method using a mode- 4.e
locked, cavity-dumped dye laser. The output from the dye
Rhodamine B methanol 2.6" 1.67 0.57"
laser (ca. 60 mW, 800 kHz) was tuned and frequency doubled 2.3h 0.43'
to give an excitation wavelength of 300 nm. Instrument
response (FWHM) was measured to be ca. 100 ps. At least Rhodamine 101 methanol 4.9" 1.48 1.w
loo00 counts were accumulated in the maximum channel Excitation wavelengths of 300 nm and 530 nm were used for lifetime
before data analysis was performed using methods previously and quantum yield measurements respectively. " This work. Ref. 18.
outlined.' The dye concentration for single photon counting ' Ref. 19. Ref. 20. Ref. 21. Ref. 22. Ref. 16. Ref. 23. Ref. 24.
experiments was lo-' mol dm-3 in each solvent. J '
Ref. 12. Ref. 25. Ref. 26.

J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89
0.1 1
0 performed using different laser excitation energies. We assign
0
Q)
6 -0.1
e S,) is complete within 1-2 ps.’ Additionally, we can rule out
B the fact that the species observed contains any significant
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0
-0.2
-0.3
400 500 600
wavelengthlnm
Fig. 2 Transient absorption spectrum measured 66 ps after laser
flash photolysis (excitation wavelength 532 nm) of Rhodamine B
(7.6 x rnol dm-3) in ethanol (m) and methanol (0).Solutions
were contained in quartz cuvettes (pathlength 1 cm) in free equi-
librium with the atmosphere at ambient temperature.
The fluorescence lifetimes (zf) of the dyes studied were mea-
sured using methanol and ethanol as solvent. All solvent-dye
combinations gave reasonable fits (as evidenced by values of
reduced xz) to single exponential behaviour indicating the
presence of one emitting species. Data from such experiments
are given in Table 1. Where comparisons from the literature
were available, it can be seen that reasonable agreement
exists between previously reported values and the data pre-
sented in this study.
Picosecond Absorption Data
The transient absorption spectra of the species observed
(66 5 ps) after laser excitation (532 nm, ca. 2 mJ per pulse) of
ethanolic and methanolic solutions of -Rhodamhe B
(7.6 x mol dm-3) are shown in Fig. 2. As can be seen,
the difference spectra exhibit maxima at ca. 430 nm and
0.4 1 /
0.1 1 -2.2
0 20 40 60 80 100
energy (arb. units)
Fig. 3 Absorbance changes observed (66 ps) after laser flash pho-
tolysis (excitation 355 nm, observation 430 nm) as a function of laser
power for ethanolic solutions of Rhodamine 6G (m) and Rhodamine
B ( 0 )at 6.7 and 6.3 x lo-’, respectively. Maximum excited singlet
state concentrations (100% beam energy) were 8.1 and 7.5 x
mol dm-3 for Rhodamine 6G and Rhodamine B, respectively.
View Article Online
4187
minima at ca. 540 nm. The spectral shape of the absorptions
shown in Fig. 2 are qualitatively similar. The difference in
observed intensity arises from the fact that experiments were
the species present in such systems to the first excited singlet
state of Rhodamine B. This assignment is made on the basis
of kinetic data (vide infra) and from the knowledge that relax-
ation to the lowest vibrational level of S1 (after excitation to
contribution from the triplet state of Rhodamine B, since the
rate for triplet-state production will equal the rate of decay of
the lowest excited singlet state which, from single photon
counting data, is ca. 3.5 x lo8 s - l (ethanol data). At a decay
of 66 ps after excitation, therefore, less than 3% of singlet
states will have been removed from solution at the time of
observation. Excited-state spectra produced upon excitation
at 355 nm of the same dye-solvent systems, after normal-
isation to peak maxima, were essentially superimposable.
Transient difference spectra were generated in exactly the
same manner for both Rhodamine 6G and Rhodamine 101
(data not shown). Maxima in the blue region of the spectrum
and bleaching in those areas where ground-state absorption
of these molecules is maximal were observed.
In any flash photolysis experiment, where quantitative
measurements are to be made, it is important to investigate
the correlation between excitation intensity and the concen-
tration of excited states thus produced. In this context, linear
plots are expected for the production of relaxed excited
singlet states in the absence of biphotonic effects, provided
there is little conversion (ca. ~ 1 0 % of) the ground state to
excited state(s). We have made such measurements for eth-
anolic solutions of both Rhodamine 6G (ground-state
concentration = 6.7 x mol dm-3) and Rhodamine B
(ground-state concentration = 6.3 x mol dm-3) after
excitation at 355 nm. The results from such experiments are
shown in Fig. 3 where the intensity observed at 430 nm for
both Rhodamine 6G and Rhodamine B are shown as a func-
tion of beam energy. The full (100%)beam energy, nominally
5 mJ, produced excited singlet-state concentrations of
8.1 x mol dm-3 in the Rhodamine 6G experiment and
7.5 x mol dm-3 in the Rhodamine B experiment, these
excited singlet-state concentrations being calculated from a
-1.4
-1.8
-2.6
0 1000 2000 3000 4000
time/ps
Fig.4 Exponential decay of the absorbance ( A ) observed
(wavelength of observation 430 nm) after laser flash photolysis
(excitation wavelength 532 nm) of Rhodamine B (7.6 x mol
dm-3) in methanol. The solid line yields a singlet state lifetime of 2.7
ns.
 View Article Online

4188 3. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

knowledge of the difference molar absorption coefficient for

the S, t S, transition at the appropriate wavelength (vide
inj-a).It should be pointed out that the slopes of the lines in 0 0 0

Fig. 3 are not directly comparable since the two experiments

were carried out using different absolute beam energies.
The assignment of the transitions observed in Fig. 2 to
excited singlet-singlet absorptions (S, t S,) was validated by
analysis of the decay of the excited states. Data is presented
(see Fig. 4) only for Rhodamine B in methanol although each i
dye has been studied in both ethanol and methanol. The exci-
tation wavelength for these experiments was chosen to be 532
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I 0
nm (quantitatively similar results were obtained when 355 nm 0.2-
was used as excitation wavelength). In a typical experiment, 0
the absorption spectra from each of 300 pulses at a given 8
delay setting was averaged and stored. The delay line was
altered so as to delay the time at which the analysis beam
interrogated the sample and a further 300 laser pulses were
delivered to the sample and the transient absorption spectra 0 20 40 60 80 100
averaged and recorded. This process was repeated for a energy (arb. units)
number of delay settings. The decay of the observed absorp- Fig. 5 The effect of increasing laser power (532 nm) on the absorb-
tion is well fitted (correlation coefficient r2 = 0.998) assuming ance due to the first excited singlet for ethanolic solutions of Rho-
the presence of one decaying species. The lifetimes observed damine 6G (4.7 x mol dmV3, wavelength of observation
from such experiments (2.7 ns) correlate extremely well with 441nm, O), Rhodamine B (7.2 x mol dm-3, wavelength of
data obtained by the (superior) technique of single photon observation 450 nm,). and Rhodamine 101 (1.5 x mol drn-’,
counting (2.6 ns). This correlation provides additional evi- wavelength of observation 462 nm, 0). Pathlength was 1 cm.
dence that the absorptions, seen in Fig. 2, arise from the first
excited singlet state of the molecule under study.
The molar absorption coefficient for the S, t S, transitions dm-3) and Rhodamine 101 (1.5 x lo-’ mol dmL3).From a
was measured by two methods. First, a comparative method knowledge of the limiting value of absorbance and the
using Ru(bpy): as actinometer was employed. Upon excita-
+
ground-state concentration of the dye, calculation of is
tion (355 nm) the charge-transfer excited state of Ru(bpy)g+ is relatively straightforward, although it should be remembered
produced with unit quantum effi~iency.~’The difference that the maximum concentration of excited singlet state mol-
molar absorption coefficient for the charge-transfer state is ecules, C,,, , which can be produced by this method is:’
reported to be -7600 dm3 mol-’ cm-’ at 450 nm.28 Solu-
tions of each dye in either ethanol or methanol and (7)
Ru(bpy)g+ in water were prepared such that they had identi-
cal absorbances (0.6 & 0.02) at the excitation wavelength (355 ~ 5 3 2is the ground-state molar absorption coefficient at 532
nm). Under such conditions, since both Ru(bpy)g+ and dye nm, I E ~ ~ ~ is( the ~ absolute
~ ~ ~ value
~ ) ofI the molar stimu-
excited states are produced with unit quantum efficiency, the lated emission coefficient at 532 nm and C, is the ground
following may be derived : state concentration.
The results obtained from both approaches are shown in
AE(Ru) A d y e ( l ) Table 2 for the ethanol data sets. As can be seen, reasonable
AE(dye) = agreement exists between the values obtained by the two
A ( R ~ ;4 5 0 nm)
methods. For subsequent interpretation of our data we have
where A q d y e ) and AER,, represent the difference molar absorp- decided to adopt those values obtained by the comparative
tion coefficients for the dye S, t S, absorption (at wave- method.
length A) and the charge-transfer excited state of Ru(bpy): +

(450 nm) respectively. A d y e ( l ) and A ( R U ; 450

), , , are the observed
absorbance values for the excited states of the dye and +
Table 2 Difference molar absorption coefficients (encl - eg el+,)
for the first excited singlet state of Rhodamine 6G, Rhodamine 101
Ru(bpy)t+ respectively as measured (66 & 5 ps after the and Rhodamine B
pulse) at wavelengths A and 450 nm after picosecond laser
photolysis (average of 300 pulses). The rates of production wave-
and decay of the charge-transfer excited state of Ru(bpy)g+ solvent dye method length dm mol-’ cm-’
are such that after 66 ps a full yield is obtained. Excitation
ethanol Rhodamine 6G (a) 428 4.2 x 104
conditions were arranged such that < l o % of the ground ethanol Rhodamine 6G (b) 428 5.4 x 104
state of either dye or Ru(bpy)g+ were converted to excited
states. The value of A q d y e ) for the peak in the blue region was ethanol Rhodamine 101 (a) 448 3.5 x 104
measured for each of the three dyes. ethanol Rhodamine 101 (b) 452 3.6 x 104
The second approach which we adopted was the so-called ethanol Rhodamine B (4 430 4.1 x 104
‘complete cQnversion’ method. In such experiments, laser ethanol Rhodamine B (b) 432 4.3 x 104
power is increased and, consequently, increasing proportions methanol Rhodamine 6G (a) 429 4,2 x 104
of the ground state molecules are converted to the excited methanol Rhodamine 101 (a) 452 4.8 x 104
singlet state by the laser pulse. Data presented above (see Fig. methanol Rhodamine B (4 428 4.0 x 104
3) show that 355 nm was not a suitable excitation wavelength
Data were obtained either (a) by a comparative method using
since insufficient energy was available. However, excitation at Ru(bpy)zf and excitation at 355 nm or (b) by maximal conversion
532 nm did show plateaux typical of such experiments and (exatation wavelength 532 nm) of ground state to excited state
data are shown (Fig. 5) for ethanolic solutions of Rhodamine (ethanol data only) corrected as per eqn. (7)in the text. Estimated
6G (4.7 x mol dme3), Rhodamine B (7.2 x mol errors *lo%.
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89 4189

80 000 Having thus obtained values for the molar absorption coef-
r
I ficients of the transitions observed at the wavelengths listed
5
.-
in Table 2, we can readily convert the data in Fig. 2 to plots
- of molar absorption coefficient us. wavelength. The absorb-
g 40000 ance changes (AA) shown in Fig. 2, at any wavelength, may
m be described by :
E
0
'=-
.-Q)
AA = (en+ 1 - cg + -+o)C,1 (8)
0 0
5 where E~ is the molar absorption coefficient of the ground
state, E~~~ is the molar stimulated emission coefficient and
8
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C E , , ~ is the absolute molar absorption coefficient for the

.-
4- S, t S, absorption process. Since E , - . ~ represents transitions
E-40 000 of an emissive nature it carries an implicit negative sign.
0
s Values of E , - . ~ were obtained from eqn. (1) given that:
-b0 0, = 3.82 x 10-2'~,,o (9)
E -80 000
C , can be calculated from a knowledge of at the
400 500 600 700
absorption maximum. We now present (Fig. 6-8) absolute
wavelength/nm spectra (i.e. E , , , - ~ ) for the S, c S1 absorption process for each
, ~ and E , , ~ (W) for Rhodamine 6 G in
Fig. 6 Plots of A & (O),E ~ - (+) of the three dyes. Also included in these figures are plots of
ethanol. (Seetext for further information.)
E~ -ro and AE.
As can be seen from Fig. 6-8, the lowest excited singlet
state spectra all show a peak in the blue region of the spec-
trum. This transition has been observed previously in the
r 6oooo 1 case of both Rhodamine 6G and Rhodamine B and assigned
r
k as an S4 t S , transition by a number of
teswarlu et aL6 have attempted to assign vibrational sub-
Venka-
I

maxima in the region 420-460 nm in the case of Rhodamine

m
0 6G. Our data, having been obtained after averaging some 500
E laser pulses, shows no spectral evidence that such submaxima
-0
3
can be distinguished.
.-Q) In the cases of Rhodamine B and Rhodamine 101, we note
0
that there appears to be some small absorption above 600 nm
sc -60000
in contrast to Rhodamine 6G.
.-w Plots of E,,, against wavelength' for Rhodamine 6G
E showed little absorption at 570 nm. We have been able to
B
2 extend the spectral region of observation to 650 nm and see
no evidence for additional absorption in that region. Since
-
b
0
the peak at 430 nm has been previously assigned as arising
E -120 000 , 1 from an S, c S, transition, it seems reasonable that the peak
400 500 600 700 present at 532 nm (in the case of Rhodamine 6G, Fig. 6)
wavelength/nm arises from an S3t S, transition. Further support for such
Fig. 7 Plots of AE (a), E~~~ (+) and (W) for Rhodamine B in assignments may be obtained by considering the energy levels
ethanol. (See text for further information.)
Table 3 Absolute molar absorption coefficients and spectral
maxima (S, + S,) for the first excited singlet state of Rhodamine 6G
and Rhodamine B

wavelength ~ , , + , / d mmol-'
~ cm-'
7 100000
Rhodamine 6 G
.-
- I
428 4.4 x 104 a
532 6.4 x 104 a
mg 50000 440 - b

E 530 3.0 x 104 c

s 562
430
3.0 x 104
5.0 x 104
c
d
.-
P)
0 530 5.0 x 104
g 0
433 7.0 x 104
8 538 1.8 x 104 e
C 440 4.8 x 104 J
.-
0
532
p -50000 1.0 x 104 @

s Rhodamine B
2 430 4.3 x 104 0

-
L
(0

1 Bp
566 3.8 x 104
-b
a

g
c
-100000 450
400 500 600 700 575 5.5 x 104 c

wavelengthjnm All measurements were performed in ethanolic solutions. Estimated

Fig. 8 Plots of AE (a), . ~ and E , , ~ (W) for Rhodamine 101 in
E ~ - - (+) errors in this work are +20%. a This work. Not measured. Ref. 9.
ethanol. (Seetext for further information.) Ref. 8. Ref. 7. Ref. 5. Ref. 10.
@
 View Article Online
4190 J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89

for Rhodamine 6G. These have been reported by Venkates-

warlu et aL6 as 18 110,28 660,36 220,40 670 and 44 730 cm-
for S,, S, , S, , S, and S, respectively. From such values it can
3.0 1
be calculated that the S, t S, and the S, + S, transitions
would be expected to appear at 443 nm and 552 nm respec-
tively, these values being close to the experimentally observed
+++++
values in this work. Similarly, the S, t S, transition would + +
be expected to appear at ca. 950 nm, a wavelength outside + +
the range we could measure. This S, t S, transition, which
would be expected at 375 nm, was also outside the spectral o
@%
a
U
++ T
I

range of observation available. In view of the similarities in

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n +
ground-state absorption spectra for each of the rhodamines o +
studied in this work, it seems reasonable to assign the

absorptions observed at 430 nm and 452 nm for Rhodamine
B and Rhodamine 101 respectively as arising from the S, t
S, transition.
It is instructive: to compare the values obtained,: in this
,
work, for values of E,, with previously reported work and to
this end such data is presented in Table 3. It can be seen that
reasonable agreement exists in the case of Rhodamine 6G
around 430 nm where values ranging from 4.4-7.0 x lo4 dm3
mol-' cm-' have been determined. However, for measure-
ments made at 530 or 532 nm, the molar absorption coeffi-
cients vary from 1.0 to 6.4 x lo4 dm3 mol-' cm-'. This wide
variation is probably not unexpected considering the range of
techniques employed to measure the same parameter. Four
groups of workers have, for example, employed 8-20 ns
pulses to measure the spectral properties of an excited state
whose lifetime is only 4 ns.3-5*9910In such experiments it is
less easy to demonstrate, with confidence, that a full yield of
the first excited singlet state is being observed at power levels
assumed to completely deplete the Rhodamine 6G ground
state. This is yet more difficult for measurements made at
wavelengths (ca. 530 nm) where stimulated emission also pre-
vents complete conversion to the S, state. The more direct
method is to use laser pulses which are much shorter than the
lifetime of the S, state. In two studies,',' one of which' was of
a preliminary nature, picosecond pulses (typically 40 ps) have
been used. Magde et al. used' a complex method of inte-
grating the fluorescence emission to calculate the concentra-
tion of S, states. Gazeau et a1.' used the more direct
approach of comparing the absorbance of the Rhodamine 6G
S, state with that of the benzophenone triplet state as stan-
dard. This is a similar approach to that employed in this
work using the absorption of the charge-transfer state of
Ru(bpy)i+. The method relies on there being effectively only
one fully populated excited state, on the timescale of the pico-
second experiment, whose molar absorption coefficient can
be accepted as a standard. Despite this more direct method,
the molar absorption coefficients were measured as 5.0 x lo4
(530 nm8), 1.8 x lo4 (538 nm7) and 6.4 x lo4 (532 nm, this
work) dm3 mol-' cm-'. The complexity of the integrated
fluorescence method for estimating S , state concentration
must allow less confidence to be placed on the absolute
values obtained in that study.7 The small difference in molar
absorption coefficients between the values reported here and
in the preliminary study by Gazeau et a/.' indicate that a
considerable degree of confidence can now be placed in a
molar absorption coefficient of 5.0-6.4 x lo4 dm3 mol-'
cm-l at 532 nm with corresponding values of 4.4 and
5.0 x lo4 dm3 mol-' cm-' at 428 nm.
The effective stimulated emission cross-section, oeff,
oeff= ( - E , - . ~ - E,,+') x 3.82 x lo-', (cm')
may be obtained from consideration of the data in Fig. 6-8
and this parameter is plotted as a function of wavelength in
Fig. 9. At 560 nm we obtained a value of oeff= 1.60 x
cm2 for Rhodamine 6G and this may be compared with
+
o +
++
++
++
a+ ++++
++++ a ++
*++
OJ
530 580 630 680
wavelengt h/nm
Fig. 9 Plots of effective stimulated emission cross-section (ceff)
for
Rhodamine 6G (O),Rhodamine B (+) and Rhodamine 101 (H).All
data is for ethanolic solutions
values of 3.2 x cm2, 1.9 x cm2 and 1.2 x
cm2 obtained in previous studies (ref. 7, 8 and 9 respectively).
A number of potential sources of error may contribute to the
discrepancies observed between these measured values. For
example, the stimulated emission cross-section [see eqn. (l)]
is calculated from a knowledge of the corrected fluorescence
emission spectrum, the fluorescence lifetime and the fluores-
cence quantum yield. Errors in the measurement of any of
these parameters will, of course, be reflected in the calculated
oeffvalues.
For Rhodamine B, this study yields a oeff value of
2.07 x cm2 (568 nm) and this can be compared with a
previous value of 0.8 x cm' (570 nm).9 The value of
oefffor Rhodamine 101 of 1.1 x cm2 (594 nm) is the
first reported value of this parameter for this molecule.
Conclusion
We have measured the excited singlet state absorption and
gain properties of three laser dye molecules by the most
direct methods available. Comparison with previous mea-
surements, where large differences have been found, indicate
that there is still some progress to be made before confidence
in these important parameters can be justified for these and
novel laser dyes.
The authors would like to formally extend their thanks to the
staff of the Center for Fast Kinetics Research for their help
and assistance during the course of these studies. In particu-
lar the contributions of Stephen Atherton, Stefan Hubig,
Tony Harriman and Paul Snowden were invaluable. The
Center for Fast Kinetics Research is supported jointly by the
Biomedical Research Technology Program of the Division of
(10) Research Resources of NIH (Grant RR00886) and by the
University of Texas at Austin. D.G.J. would like to acknow-
ledge the award of an SERC CASE Studentship. Further
financial support from British Nuclear Fuels plc is gratefully
acknowledged.

J. CHEM. SOC. FARADAY TRANS., 1993, VOL. 89
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Paper 3104313D; Received 21st July, 1993