29 June 2001

Chemical Physics Letters 341 (2001) 535±539

www.elsevier.nl/locate/cplett

Non-monotonic decay of transient infrared absorption in

dilute HDO=D2O solutions
G. Gallot a, N. Lascoux a, G.M. Gale a, J-Cl. Leicknam b,*,
S. Bratos b, S. Pommeret c
a
Laboratoire d'Optique Quantique, Ecole Polytechnique, Route de Saclay, 91128 Palaiseau Cedex, France
b
Laboratoire de Physique Th eorique des Liquides, Unite de Recherche Associee au CNRS, Physique Theoretique des Liquides,
Universit e Pierre et Marie Curie, Case courrier 121, 4 Place Jussieu, Tour 16, 75252 Paris Cedex 05, France
c
CEA/Saclay, DSM/DRECAM/SCM/URA 331 CNRS, 91191 Gif-sur-Yvette Cedex, France
Received 7 December 2000; in ®nal form 15 February 2001

Abstract
Transient infrared absorption of diluted HDO=D2 O solutions is measured with 150 fs laser pulses. The signal in-
tensity decays in a heavily non-exponential way, and its variation is often non-monotonic; no quantum beats are
observed. These e€ects are ascribed to the simultaneous presence of solvent and population dynamics in low lying
vibrational states, and to a partial cancellation of the bleach and absorption intensities. Ó 2001 Elsevier Science B.V.
All rights reserved.

1. Introduction and excited electronic states of the system is ob-

The short time relaxation of photoexcited
molecules in dense phases, immediately after ex-
citation, has been a subject of considerable inter-
est. Most often the excitation is in the visible
spectral range. If the laser pulse duration is com-
parable to the vibrational oscillation period, mol-
ecules are excited coherently and they oscillate in
phase. Damped quantum beats may then be ob-
served by the help of various non-linear spectros-
copies such as spontaneous ¯uorescence,
transmission correlation, transient absorption,
transient birefringence and dichroism. Informa-
tion concerning vibrational motions in the ground
*
Corresponding author. Fax: +33-1-44275100.
E-mail address: jcle@lptl.jussieu.fr (J.-C. Leicknam).
0009-2614/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 1 ) 0 0 5 2 4 - 3
tainable in this way.
The laser excitation may also be infrared.
However, a number of technical diculties had to
be overcome to proceed further. The published
work mainly refers to the diluted solution
HDO=D2 O, an isotopic variety of liquid water.
The OH


O motions were `photographed' in real
time, but no oscillations were observed: they are
too strongly damped to be `seen' [1,2]. The loss of
the initial phase coherence is due to three mecha-
nisms: the population relaxation, spectral di€usion
and orientational relaxation. (i) The vibrational
population relaxation time sp , was measured by a
number of authors [1±4]; values between 1 and 2 ps
were reported. It exhibits a pronounced tempera-
ture [5] and frequency [6] dependence. (ii) Spectral
di€usion evolves over time scales of the order of
sX , the mOH frequency shift correlation time; it was
536 G. Gallot et al. / Chemical Physics Letters 341 (2001) 535±539
found equal to 0.7±0.8 ps, both by theory [7] and
experiment [1,2]. (iii) The orientational relaxation
time so was provided by the NMR and molecular
dynamics studies; values of the order of 2.5 ps were
proposed in the literature [8±11]. Although there
are still controversies, there is an overall agreement
on this picture.
The purpose of this Letter is to reexamine the
decay of the transient infrared absorption of di-
luted HDO=D2 O solutions with 150 fs resolution.
A large number of pump and probe frequencies
were employed. The absorption was shown to
decay in a heavily non-exponential way and often
is non-monotonic. The `reading' of the spectra is
dicult, and their interpretation requires a con-
siderable theoretical e€ort. The observed e€ects
are ascribed to the simultaneous presence of sol-
vent and population dynamics, and to a partial
cancellation of the bleach and absorption intensi-
ties. For earlier work on this problem, see [12].
2. Experiment
The experimental set-up employed was de-
scribed elsewhere [1,2]; it is only sketchily
redescribed here. Its central element is a titanium±
sapphire ampli®er which drives an optical para-
metric ampli®er system producing a 10 lJ pump
pulse and a 1 lJ probe pulse. They are both
tunable from 2800 to 3800 cm 1 , have a duration
Fig. 1. Time-resolved pump±probe infrared spectra of a diluted HDO=D2 O solution. The wave number of the pump is 3510 cm 1 , and
those of the probe are 3510, 3380, 3360, 3340, 3320 and 3300 cm 1 . Experiment is illustrated in Fig. 1a, and theory in Fig. 1b.
of 150 fs and a spectral width of 65 cm 1 . The
angle between the pump and the probe beams,
polarized in the same direction, is 15°. The pump is
chopped at 500 Hz to obtain di€erential spectra,
with and without excitation.
Temporal evolution of the system was followed
over several ps. Three pump frequencies X1 were
employed at 3510, 3420 and 3300 cm 1 ; and in
each of these three cases, spectral transients were
recorded for a large set of probe frequencies X2 .
Typical results are illustrated in Fig. 1a; the
following observations merit attention. (i) Initial
decay of the signals is always heavily non-
exponential. A narrow component with a width of
the order of 1 ps coexists with a broad component
extending over 2 ps or more. (ii) The decay is not
necessarily monotonic; an overshoot from the
initial absorption to the ®nal bleach is often
observed. (iii) The maxima of the bleach and
absorption transients do not coincide. The
absorption component peaks at earlier times than
its bleach counterpart; however, the positions of
their maxima depend distinctly on X2 . (iv) The
spectra do not vary very much with the excitation
frequency X1 .
3. Theory
The theory is based on an expression for the
pump±probe signal recently proposed by Bratos
 G. Gallot et al. / Chemical Physics Letters 341 (2001) 535±539
and Leicknam [13]. If S…X1 ; X2 ; s† is de®ned as
temporally integrated probe absorption in pres-
ence of the pump minus the probe absorption in its
absence, then
S…X1 ; X2 ; s†
Z 1 Z 1 Z 1 Z 1
2 /2 …t†, independent of each other.
ˆ 3 Im dt ds1 ds2 ds3
h 1 0 0 0
 hE_ 2 …r; t† E…r; t s3 †E…r; t s3 s2 †
 E…r; t s3 s2 s1 †iE

 hM…0†‰M…s1 †‰M…s1 ‡ s2 †M…s1 ‡ s2 ‡ s3 †ŠŠiS :
…
Eq. (1) contains two 4-time correlation functions:
the correlation function of the total and probe
electric ®elds E and E2 , and that of the electric
dipole moment M of the system. The average h iS is
over the states of the non-perturbed liquid sample,
and the average h iE is over all possible realizations
of the incident electric ®elds. The symbol [ , ] de-
notes a commutator, the dot a time derivative and
s the time delay of the probe with respect to the
pump. For a description of higher-order correla-
tion functions, see [14].
The present problem was modeled as follows. (i)
The spectrally active OH vibration of a HDO
molecule is assimilated to a three-level quantum
system perturbed by stochastic solvent±solute in-
teractions; the energy level diagram is illustrated in
Fig. 2. (ii) The dipole moment of the molecule is
governed by the equation
dM i appears as a sum of terms proportional to
ˆ ‰H ; M Š C M; …
dt h
Fig. 2. Low lying OH stretching energy levels of an HDO
molecule. The frequency of the v ˆ 0 ! v ˆ 1 transition is
equal to X01 , and that of the v ˆ 1 ! v ˆ 2 transition is equal
to X12 .
537
where H is an adiabatic Hamiltonian of the liquid
mixture, and C the Pauli relaxation matrix. (iii)
The correlation between vibrational and rotational
motions is neglected. (iv) The pump and probe
electric ®elds E1 …X; t† and E2 …X; t† are given a
Gaussian form and random phases, /1 …t† and
The detailed calculations are described in [13];
they are only sketchily reproduced here. The di-
pole moment correlation function hM…0†‰M…s1 †;
‰M…s1 ‡ s2 †; M…s1 ‡ s2 ‡ s3 †ŠŠi is calculated by: (i)
determining the time evolution of M…s† by the help
of Eq. (2), (ii) employing the cumulant expansion
1† theorem and (iii) considering time scales inherent
to this problem. The resulting correlation function
then appears as a sum of terms proportional to



1
a…s2 † exp 2
s21 ‡ s23 b  s1 s3 b…s2 ‡ s3 † ; …3†
where a…s† ˆ hu2 …0†u2 …s†i is the rotational corre-
lation function of the unit vector ~u along the OH
bond of HDO; b…s† ˆ hx…0†x…s†ic is the frequency
shift correlation function, where the index c indi-
cates a cumulant, and b ˆ b…0†. In conformity
with computer simulation results of [7,9±11], the
decay of a…s† and b…s† is supposed to be mono-
exponential with time constants so and sX .
The electric ®eld correlation function hE_ 2 …r; t†
E…r; t s3 † E…r; t s3 s2 † E…r; t s3 s2 s1 †iE
may be evaluated by (i) decomposing E1 and E2
into individual exponentials, (ii) neglecting non-
secular contributions to it and (iii) treating the
random phases /1 …t† and /2 …t† by the help of the
cumulant expansion theorem. The ®nal result then
2†
exp… c…t12 ‡ t22 ‡ t302 ‡ t402 ††
1 2 1 2
 exp… …t
2 1
t2 † / …t
2 3
t4 † /†; …4†
where t1 ; t2 ; t3 and t4 are the various combinations
of times t; t s3 ; t s3 s2 ; t s3 s2 s1 .
Moreover, t0 ˆ t ‡ s, / ˆ h/_ 21 i ˆ h/_ 22 i whereas c
determines the temporal width of the pump and
probe electric ®elds.
The last step of the calculation consists in
performing multidimensional integrations over
t; s1 ; s2 and s3 in Eq. (1). They were realized
numerically by the help of a specially written
algorithm. No approximations were required to
538 G. Gallot et al. / Chemical Physics Letters 341 (2001) 535±539
do it; in particular, the overlap of the pump and
probe pulses was fully accounted for. The spectra,
calculated by using this model, are shown in
Fig. 1b; the agreement with experimental data of
Fig. 1a is extremely satisfactory.
4. Discussion
The following picture of non-monotonic pump±
probe absorption in HDO=D2 O is suggested by
this work. Let us ®rst suppose that the lowest ex-
cited vibrational level is non-degenerated and well
isolated from all other states (Fig. 3a); the decay of
transient absorption is then basically mono-expo-
nential, with a time constant equal to the popu-
Fig. 3. Decay of transient infrared absorption (schematically).
(a) The excited vibrational state is isolated; the decay of the
signal exhibits the time sp . (b) The excited state takes part in a
continuous sequence of excited vibrational states; the signal
decays on two time scales, sp and sX . (c) There exist two con-
tinuous sequences of vibrationally excited states; depending on
the choice of the pump and probe frequencies, X1 and X2 , the
signal intensity may either decrease or increase with the time
delay s.
lation relaxation time sp . The situation is di€erent,
if this state is replaced by a continuous sequence of
excited vibrational states (Fig. 3b). The pump then
generates a wave packet propagating in the liquid
at scales of the order of the solvent relaxation time
sX . Transient absorption will exhibit two decay
times, sp and sX . Let us ®nally assume that the
vibrator contains two continuous, well-separated
sequences of states (Fig. 3c). The pump±probe
signal remains comparable to that just described,
but may have a positive or a negative amplitude
(induced absorption or bleach). A partial com-
pensation of these two components of the signal
may stop its decline, or even produce its ampli®-
cation! This last case is closely related to the ex-
perimental reality. As the OH vibrational
frequency depends on the OH


O bond length,
the continuous sequences of excited states in Fig. 3
are those of individual OH vibrators, captured in
OH


O bonds of di€erent lengths.
The observed material entirely conforms to this
picture; see Fig. 1a. The short time component of
the signal is generated by the solvent relaxation
and decays with a time sX ; and its long time
component is due to the population relaxation and
decays with a time sp > sX . Their relative intensi-
ties are X1 , X2 dependent; the solvent relaxation
dominates if X1 X2 ˆ 0 or X1 X2 ˆ X01 X12 ,
whereas the population relaxation dominates
otherwise; this point is discussed in [15]. Finally,
analyzing computer generated data con®rms that
the non-monotonic time evolution of S…X1 ; X2 ; s†
mainly results from a competition between the
bleach and the induced absorption.
The calculated values of time constants are
sX ˆ 0:7 ps, sp ˆ 1=C ˆ 1:3 ps and so ˆ 2:5 ps;
they are exactly the same as those given by [1,2]. It
is also noteworthy that a good agreement between
theory and experiment was reached by maintain-
ing the population relaxation time sp equal for the
v ˆ 1 $ v ˆ 0 and v ˆ 2 v ˆ 1 transitions;
these two times are probably not too di€erent in
reality. The theory is the simplest for the 3510
cm 1 series; additional degrees of freedom, such as
OH bending, are involved in the 3420 cm 1 and
3300 cm 1 series.
Comparison with the literature data brings out
the following points. (i) Although shortly men-
 G. Gallot et al. / Chemical Physics Letters 341 (2001) 535±539
tioned by Woutersen and Bakker [12], it is the ®rst
time that non-monotonic decay of infrared ab-
sorption is fully examined for a large number of
pump and probe frequencies. However, this e€ect
has already been discovered and interpreted in the
visible spectral region by Kimura et al. [16], Sch-
wartz and Rossky [17] and Pommeret et al. [18].
(ii) The OH motions are quantum mechanical here
and in [12]. The remaining degrees of freedom are
treated by classical molecular simulation in this
work, and by employing the semi-empirical
Brownian oscillator model in Woutersen±Bakker's
paper. (iii) The presence of two time scales sX and
sp , as well as the cancellation of bleach-induced
absorption intensities, makes `reading' of the ex-
periment dicult. Nevertheless, correctly inter-
preted, it provides new values for sX : measuring
solvatochromic shifts no longer is the only way of
studying solvent relaxation.
Acknowledgements
The authors would like to thank the GDR 1017
of the CNRS for its support during this work. The
Laboratoire d'Optique Quantique is a `Unite
Mixte de Recherche' no. 7645 of the CNRS and
the Laboratoire de Physique Theorique des Liqu-
ides is a `Unite Mixte de Recherche' no. 7600 of
the CNRS.
539
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