F. García-Golding Vol. 73, No. 1/January 1983/J. Opt. Soc. Am.

59

Spectral-diffusion effects in polarization spectroscopy

F. García-Golding
instituto Venezolano de investigaciones Científicas, Centro de Física, Apartado 1827, Caracas 1010A, Venezuela

Received (uly 20,1981; revised manuscript received August 11,1982

The effect of cross relaxation on the third-order nonlinear susceptibility, x ( ^ 2 » « l , — u¡\, 0)2), describing polar-
(3) —

ization spectroscopy experiments is calculated with a density matrix formalism. By using a model of inhomo-
geneously broadened two-level systems with a reservoir state and allowing for cross relaxation within the inhomo-
geneous line, we find that both the ratio of the máximum signal at wi = (¿2 to the background and the broad compo-
nent resembling the absorption band depend on the cross-relaxation rate. Also, one additional component with
a characteristic width of the order of the spectral-diffusion rate r¡ is expected to appear, depending on the valué
of this parameter. Furthermore, we estímate from published data [Phys. Rev. A 17, 1439 (1978)] the product of
the transverse-relaxation time times the cross-relaxation time T0T3 to be 0.014 psec for cyanine dye and 0.0009
2

psec for malachite green oxalate.

2

Recent nonlinear optical techniques, such as resonant Ray- tween theory and the experimental data. In this simplified
leigh-type optical mixing and polarization spectroscopy
1-3 model, we have neglected the potentially interesting phe-
( P S ) , have made it possible to measure, in the frequency
4,5 nomenon of rotational diffusion.
domain, the homogeneous linewidth and decay rate of inho- The spectral-diffusion model introduced by Mourou and 6

mogeneously broadened electronic transitions involving states extended by Yajima is used to perform the calculations of the
1

that decay in the subpicosecond range. The absence of any appropriate third-order susceptibility for PS. In this model
wave-vector matching condition in P S makes this technique the probability that a molecule changes its transition fre-
more attractive than the Rayleigh-type technique. In addi- quency from oír/ to a valué withintoo~ too + dtoo in unit time
tion, the detected signal has a contribution from the steady- isg(wo)T3 dtoo, whereg(ton) is the molecular distribution.
-1

state change of the populations (hole burning) that permits The nature and shape of this distribution is attributéd to
the extraction of the transverse relaxation time T in a simple
2
two random quantities obeying a Gaussian distribution, that
way. is, the different solvent cages and the different configurations
In a P S experiment, the intensity and frequency-dependent adopted by the solute molecule. As the work of Mourou has
dichroism and birefringence are created by a pump wave and shown, the adequacy of this hypothesis has already been
probed by a second wave at frequencies a>i and (¿2, respec- tested in the case of cryptocyanine dye. 6

tively. In order to explain these optical anisotropies in organic The model system considered is shown in Fig. 1, where y , a

dye solutions, Song et al. used an ensemble of two level sys-

4 7 b , and y are the population decay rates and y¿ = T ~ and
c 3 l

tems with a distribution of resonant frequencies for modeling y i = g(too)T3 (per unit to ) are the cross-relaxation rates for
_1 0

the absorbing species. In that case, the expected line shape direct spectral-diffusion and inverse processes, respectively. 7

consists of two components, the broader having a width twice Two incident light waves of frequencies toi andto2are nearly
the homogeneous linewidth (21^2 = 2 / T ) and the narrower
2 resonant with the transition (a - * 6) assumed inhomo-
having a width related to the population-decay rate ( 1 / T i ) . geneously broadened. The level (c) is far from resonance with
Furthermore, the ratio of the máximum signal observed at a>i both toi and o>. The density matrix equations describing this
2

— 0)2 = 0 to the background level that is due to the component system are
of the width 2T2 is predicted to be 4:1. However, the pre-
sented experimental data generally show lower valúes: the
4

ratio varies from 3.2:1 for malachite green oxalate in water 7 (HabPba — PabHba) + "YaPbb + y Pcc c ~ ~~
di h I3

solutions to less than 2:1 for cyanine dye in high-viscosity

solvents. It is also concluded that the optical transitions in + ~^~ I Paa(w. t)dto', (1)
these organic dyes are nearly homogeneous. This is incon- 1 3 JO
sistent with recent Raleigh-type optical-mixing experi- "Pfcfe _ l tu ij Pbb
ments. ~J~ ~ 7 \HbaPab — Pb n b) a a - ybPbb - y a Pbb ~ ~
dt h
3
T3
It has been learned from hole-burning and optical-mixing s(to) r™
experiments that cross relaxation is always present in systems
6 + ~ p (<»',t)da',
bb (2)
TQ JO
such as organic dyes, that is, a molecule can migrate freely to
any place to experience varying environmental molecular
Paa + Pbb + Pee = g(<>>), gMdto = 1, (3)
fields, which causes random shifts in transition frequen-
cies.
It will be seen that the inclusión of spectral diffusion within dpba _ dPab* 1 1 \ . • \\
u

~T~ - = 7 HbaKPaa ~ Pbb) ~ (1 2 + l<¿0)Pba, (4)

the homogeneous broadening yields a better agreement be-
di di h

Reprinted from Journal of the Optical Society of America, Vol. 73, page 59, January 1983
Copyright © 1983 by the Optical Society of America and reprinted by permission of the copyright owner.
60 J . Opt. Soc. Am./Vol. 73, No. 1/January 1983 F. García-Golding

The complex macroscopic nonlinear polarization is given

lb> 1- •Ti c; by

(i
P(3)(to ) = N 2 </i 6P6a >dto ,
a (3) 0 (8)

where N is the density of the absorbing species and the

brackets denote an ensemble average over the initially iso-
UJ0
•lc> tropic orientational distribution. Then, after integration,
2TT¿
P ( 3 ) ( 0 ) 2 ) = ~^ToN (Hab(Hba • E ) \(l 2 ba • E i | ) F(A), 2 (9)

where
la>-
F(A) = FAA) + F (A), 2

1 i
Fig. 1. Energy-level scheme. +
r + ÍA r r x s x r, + ¿A
H b a = H * = -n a b ba • ( E ^ - " " ' + E e-»* 2 + c • c), (5) i
where r is the transverse-relaxation rate, E i and E are the
2 2
( r + ¿A)(r + ¿A)
x 2r + s 2 ¿A
electric-fíeld amplitudes of the líght waves, Hba is the electric i
- r ) + •r ( r - r )
F (A) =
2
dipole matrix element, and g(o>o) is the distribution of reso- r + ¿A r r
4 x x 3 s s 3

nant frequencies describing the total absorption band.

i
All levéis except (a) are assumed unpopulated at equilib- +
rium, and, for the sake of simplicity, a Lorentzian shape of ( r + iA)(r - r + ¿A)
x x 3

width T (HWHM) will be used for g(to). Also, the following

4 I r ,3 r D 1

condition will be used: (r, + iA)(T, r + 3 ¿A) ( r + ¿A)

4

T » r ,7a,
4 2 7fc, 7 c - (6) i i
Solving Eqs. (l)-(5) in the rotating-wave approximation r (r -r )\rx r - r s 3 s x

by the method of successive approximations gives the fol- í^

lowing third-order solution of p at the probé frequency: b a ( r + ¿A)(r - r + ÍA)
x s 3

-¿Qifeq-E^lMfea-Exl 2
I i
(3)
Ph, (W ) =
2

h*T [ r + ¿(too ~ to )]
4 2 2
x \ r + ¿A ' r - r + ¿ A ;
s x 3

r + r - r
x /1 i s D where condition (6) was used to perform the calculation.
x — — — - + — + — 5
The third-order nonlinear susceptibility is defined, as usual,
r r \D DÍ x s 2

by the following relation between the complex field ampli-

i i r D
tudes:
v + ¿ A r + ¿A ( r + ¿A)(r + ¿A
x s x s

P¿< >(to ) = 6
3 2 X ( 3 W - w , to -toj, 2 1( to ) 2 EjíuJEkHwJEiiwo).
i i
- 2flT3g(to ) 0
The two components necessary for PS, i.e., X 1 2 1 2 and X 1 1 2 2 ,
r (r - r ) r(r - r ) x x 3 s 3

are proportional to the function F( A) introduced above. The

i
F i ( A ) is identical with the one obtained by the result of Song
( r + ¿A)(r - r + ¿A)
x s 3
et ai, except that the population rates are replaced by effec-
i tive rates that take into account'spéctral diffusion. This part
+ •(r + ¿A)(r r + ¿A)
s 3
broadens as cross relaxation increases. The F part origi- 2

nating from inverse spectral diffusion has resonant denomi-

1
- 2xr g(to ) 3 0
nators, such as T - T + Í A and T — T + ¿A, which are
x 3 s 3

r ( r - r >rx s 3 s independent of T . In addition, it has a background compo-

3

nent that follows the absorption line. When T increases, 3

(T x + iA)(T s - r + ¿A) 3
F ( A ) increases and reaches a plateau in contrast to contin-
2

uously decreasing F i ( A ) . Let us assume that

i i
Q— ÍCÜ2Í (7)
\r s + ¿A 'r - r + x 3 ¿A/J r »r ,
4 2 r 3 » 7 i , > 7 . > C 7 ; Q

where then
D¡ = T + i(to - 2 0 to ),£ (i = 1,2), Tz, = 7 - Q 7 c ,
r ~ r ,
x 3

r = 7c
x + y a + jb + — =r , s r ~ r , s 3
T,' 1 3
r - r =
x 3 y, e

r = —-,
3 A =to!- co2.
i3 r, - r « 3 7 6 . (10)
F. García-Golding Vol. 73, No. 1/January 1983/J. Opt. Soc. Am. 61

From Eq. (9), we can see that 1.0

2
F (0)
x c* F (0) 2 di)
r r '
2 3 r r '
4 c

then 8

F (O) ^ r r
2 2 3
(12)
>i(0) ~ r ' 4 T c

The assumption that y , 7 6 » 7 c leads to a

R _ i r r 2 3

2 r 4 7 c

Depending on the valúes of the different relaxation times in-

volved in Eq. (12), the inverse spectral-diffusion effect can
become as important as the direct one.
The appearance of the spectra for a P S experiment pa-
rameterized by T is plotted in Fig. 2, which shows that, for
3

low cross-relaxation rates, the central peak broadens. Nev-

ertheless, at larger valúes of T a narrow peak will appear in 3

the spectra with a width of the order of y . This peak is c

precisely the contribution from the inverse spectral-diffusion

process, specifically, the resonant term T — T + ¿A. x 3

Figure 3 shows the whole appearance of the spectra pa-

rameterized by T in which the following three regions can be
3
Fig. 3. Same as Fig. 2 but on a larger frequency range, showing the
intermedíate región and the broad component.
observed: the narrow peak that was mentioned before, having
a width related to the slowest population decay time; an in-
exhibit only two time scales: 7 and ( 2 r ) for T / r « C _ 1 2 _1 3 2
termedíate región related to 2r , T , , and T (more noticeable
1, and 7
2 x
and T for T a¡ T . We show below that, in the
for r / r = 0.2 in Fig. 3); and a wider component similar to
C _ 1 4 _ 1 3 2

case in which T ca T , the contrast of the central peak with

3 2

the absorption band (more noticeable for r / r = 0.2, 0.7 in

3 2
3 2
respect to the wider component can provide us with infor-
Fig. 3).
mation about the product T2T3.
For valúes of T such as T / r = 0.2 in Fig. 3, the width of
3 3 2
In light of this model, the central peak observed in P S ex-
the intermedíate región approaches T . It is the contribution 3
periments on malachite green oxalate in water solutions and
of the oscillation of the population that comes from F\, and
cyanine dye on high-viscosity solvents should be interpreted
in that case, the spectra will clearly show three characteristic
as the contribution of the inverse spectral-diffusion process.
times: 7 , ~ r , and r . For very low ( r / r « 1) or
C _ 1 3 _ 1 4 _ 1 3 2
It is consistent with the following facts:
very high ( T a* T ) spectral-diffusion rates, the spectra will
3 2

(1) The decay rate deduced from the width of the central
peak in malachite green agrees with the time-domain exper-
iment of Ippen et al., and the faster transient that is due to
9

cross relaxation should not be noticeable in these experi-

ments.
(2) The ratio of the máximum signal of A = 0 to the in-
tensity of the background component is lower than 4.
(3) There is a broad component similar to the absorption
band.

Within the approximations expressed in Eqs. (10), and with

yc « | A| « 7 r , r , T , we get
6 > 2 3 4

Re F i ( A ) F,(0),
ImFi(A) V A [(2r + r ) / r r ] F ( o ) « F M ,
8 2 3 2 3 1

Re F ( A ) 2
i / r 7 c = y F (o),
4 2 2

Im F ( A )
l / r A « F (0).
2
4 2

Then
F(0) 2 íFi(0) + F (0) ja 1 + Ry 2

= 12 (13)
F(A) Fi(0) + F (0)/2. 2 + RJ2

and
Fig. 2. Computer plot of |F(A)/F(0)| for 0 < A < I0y . V is
R = 2 S/A - 1
2 c 3

considered a parameter. The solid line is for r¿ < y ; the dashed line c
r r 2 3
(14)
is for Ta > 7,.. VA i\y c
62 J. Opt. Soc. Am./Vol. 73, No. 1/January 1983 F. García-Golding

We now analyze the P S experiment of Song et al. on 1,3'- previous experiments that use a different technique, such as
diethyl-2,2' quínolylthía-carbocyanine iodide (DQCI) in light Rayleigh-type optical-mixing spectroscopy.
of this model. It is reasonable to assume that the width of the Experiments are in process to detect the predicted com-
central peak, i.e., Ao>/27re =Ü 3 c m (FWHM) corresponding
_ 1 ponent, so that not only T T but also T and T can be de-
2 3 2 3

to a time of ~3.4 psec, is the longest relaxation time y . The c - 1 termined. Such a search is important because it is necessary
time related to the inhomogeneous distribution l / r taken 4 to have at least two independent techniques with which to
from the absorption data of Yajima for T = AÍO/2-ITC = 818 4 measure in the subpicosecond regime in order to test a specific
cm- (HWHM) is 1/T = 0.0064 psec. From the P S experi-
1 4 model for relaxation mechanisms in the condensed phase.
ment, A 2; therefore, from Eq. (14), y T /T T 1.41 and c A 3 2 Note added in proof: During the writing of this paper, 11

T T
2 1.4 X 10- psec .
3 2 2 we became aware of a recent paper in which the influence of
The Rayleigh-type optical-mixing experiment of Souma et cross relaxation for a two-level system in P S spectroscopy was
al. on DQCI in ethanol, although performed with a different
3 considered. Attention was focused on the disappearance of
solvent, is in reasonable agreement with our estímate. They the information about T (specifically, the broadening of the
2

report T between 0.1 and 0.2 psec and T / T Y in the range

2 2 wing of the spectra connected with the steady-state change
0.4-1 psec, where 1/7Y = VTi + 1 / T ^ 1 / T . Unfortu- 3 3 of the population hole burning) for increasing spectral-dif-
nately, for the case of malachite green, we do not have a fusion rate. Our emphasis is on the possibility of obtaining
Rayleigh-type optical-mixing experiment to compare with, information about the product T T and, under certain con-
2 3

but we can estímate the product T T from the P S experi- 2 3 ditions, T and T separately even in the presence of relatively
2 3

ment. Repeating the same arguments that were previously high spectral-diffusion rates.
applíed to DQCI with A 3, y ~ 1.2 psec, and l / r =
c l 10 4

0.0063 psec, weobtainR ^ 8.6and T T = 9 X 10~ psec for 2 3 4 2

malachite green oxalate. REFERENCES

This analysis also implies that the relaxation rate extracted 1. T. Yajima and H. Souma, "Study of ultrafast relaxation processes
from the narrow component in a P S experiment is not always by resonant Rayleigh-type optical mixing. I . Theory," Phys.
comparable with the effective relaxation rate ( 1 / T i + 1 / T ) 3
Rev. A 17,309-323 (1978).
2. T. Yajima, H. Souma, and Y. Ishida, "Study of ultrafast relaxation
= 1/TY measured by optical-mixing experiments, which 1,2
processes by resonant Rayleigh-type optical mixing. I I . Ex-
explains the apparent contradiction pointed out by Song et periment on dye solutions," Phys. Rev. A 17, 324-334 (1978).
al. when they compared both techniques. In the interpre- 4 3. H. Souma, T. Yajima, and Y. Taira, "Ultrafast relaxation study
tation of these experiments, the population-decreasing effect, by resonant Raleigh-type mixing spectroscopy using picosecond
or direct spectral diffusion, was taken into account; the inverse light pulses," J. Phys. Soc. Jpn. 48, 2040-2047 (1980).
4. J. J . Song, J. H. Lee, and M. D. Levenson, "Picosecond relaxation
spectral diffusion is not expected to influence the line shape measurements by polarization spectroscopy in condensed
except for | A | < 1/Ti (see, for example, Ref. 3). phases," Phys. Rev. A 17,1439-1447 (1978).
The previous analysis was done under the hypothesis that 5. J . H. Lee, J . J . Song, M. A. F. Scarparo, and M. D. Levenson,
the homogeneous linewidth is small compared with the dis- "Coherent population oscillations and hole burning observed in
Sm :CaF using polarization spectroscopy," Opt. Lett. 5,196-198
+ 2
tribution of resonant frequencies; if we drop that restriction (1980).
we need to make a convolution with the line shape of the ab- 6. G. Mourou, "Spectral hole burning in dye solutions," I E E E J .
sorption band, and the spectra will depend not only on A but Quantum Electron. QE-11,1-8 (1975).
also on the position of the pump and probé frequencies within 7. The división of the spectral diffusion into direct (population-
the inhomogeneous distribution. decreasing effect) and inverse (population-increasing effect)
diffusion is not meant to imply the existence of two different
In conclusión, we have made a study of the expected line physical effects. It is rather a convenient way of separating the
shape in a PS experiment in which cross relaxation within an population-changing effects of spectral diffusion on a selected
inhomogeneous line is considered. The features exhibited pair of levéis with transition frequency a>o-
by the región around the narrow component of the spectra and 8. A parallel expression was obtained in Ref. 3 in relation to Ray-
leigh-type optical mixing.
the existence of a broad component similar to the absorption 9. E . P. Ippen, C. V. Shank, and A. Bergman, "Picosecond recovery
band are explained. Also, one additional component with a dynamics of malachite green," Chem. Phys. Lett. 38, 611-614
characteristic width of the order of T is expected to show, 3 (1976).
depending on the valué of the spectral-diffusion rate. It was 10. An absorption spectrum was made in malachite green with a Cary
shown that the product T T can be estimated from the
2 3
17DI spectrophotometer in order to obtain the quantity r . 4

11. Y. Taira and T. Yajima, "Cross relaxation effect in polarization

contrast of the narrow peak with respect to the broader spectroscopy of condensed phases," J . Phys. Soc. Jpn. 50,
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