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Four-wave mixing with femtosecond pulses

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2009 Phys. Scr. 2009 014037
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IOP PUBLISHING

PHYSICA SCRIPTA

Phys. Scr. T135 (2009) 014037 (3pp)

doi:10.1088/0031-8949/2009/T135/014037

Four-wave mixing with

femtosecond pulses
H Skenderovic
Institute of Physics, Bijenicka cesta 46, HR-10001 Zagreb, Croatia
E-mail: hrvoje@ifs.hr

Received 8 January 2009

Accepted for publication 12 January 2009
Published 31 July 2009
Online at stacks.iop.org/PhysScr/T135/014037
Abstract
The recent development of noncollinear optical parametric amplifiers (NOPAs) has equipped
many laboratories with widely tunable, spectrally broad ultrashort laser pulses with a duration
of 1530 fs. The present work deals with sub-20 fs pulsed degenerate four wave mixing
(DFWM) on high-frequency vibrational levels in all-trans--carotene. The observed
wavepacket motion on the electronic ground state revealed fast oscillating vibrational modes
whose frequencies and time development were measured. The coherent control in an open
loop is demonstrated by appropriate phase shaping of the pulses.
PACS numbers: 87.15.ht, 42.65.Hw, 78.47.jj, 33.20.Tp
(Some figures in this article are in colour only in the electronic version.)

are monitored by the intensity of the fourth beam for different

time delays. This mechanism relies on impulsive Raman
scattering [5], which implies the shortness of the pulses
compared with the vibrational periods. Since the periods of
the monitored vibrations are in the 2030 fs range, the pulse
duration in the sample has to be adequately short.
Moreover, it is possible to prepare the initial state just in
a single, selected vibrational mode by appropriately shaped
pulses, which is demonstrated for three high-frequency
vibrational modes in -carotene. This mode selectivity could
be further utilized in mode-selective chemistry.

1. Introduction
The past decade and a half has witnessed a rapid increase in
the number of real-time molecular dynamics investigations
using ultrashort pulses [1, 2]. In these investigations,
third-order nonlinear techniques were increasingly employed.
On the femtosecond timescale, of particular interest are
degenerate four-wave mixing (DFWM) measurements,
because they require just one laser source.
The experiments are configured by sending three laser
beams into the sample and making them overlap spatially
in the interaction region. Concerning the spatial and time
ordering of the pulses, the work described here is done
in transient grating arrangement where two pulses come
simultaneously and the third beam is advanced or delayed
in time in a controllable manner. The input beams (wave
vectors k1 , k2 and k3 ) are directed in a folded boxcar geometry
and the signal is detected in the kS = k1 k2 + k3 direction.
The object of this work is to excite, measure and control the
vibrational wavepacket motion in the ground electronic state
of all-trans--carotene in the solution. The paper also presents
a summary of the already published [3, 4] experiments and
some new results.
The first two beams prepare the system in a coherent
superposition of vibrational states, which evolves in time, and
the third beam interrogates the evolved state and creates a
fourth wave, the signal. The dynamics of the prepared state
0031-8949/09/014037+03$30.00

2. Experiment
The laser system is based on a fibre SErF oscillator whose
weak output at a repetition rate of about 37 MHz is amplified
by a chirped-pulse regenerative amplifier (Clark CPA-2010).
The whole system is enclosed in a single housing that
improves the stability and delivers approximately 700 J
pulses at a 2 kHz repetition rate at 775 nm. A part of this beam
(200 J) pumps the noncollinear optical parametric amplifier
(NOPA) that can be tuned from 480 to 700 nm. The output of
the NOPA is spectrally a very broad pulse having an energy
of about 10 J, whose duration can be compressed by an
additional prism compressor down to about 17 fs.
After the compressor, the beam was split into three
beams 1, 2 and 3 as shown in figure 1. On the way to the
1

2009 The Royal Swedish Academy of Sciences

Printed in the UK

Phys. Scr. T135 (2009) 014037

H Skenderovic

Table 1. High-frequency vibrational modes.

Ground state vibrations

Frequency (cm1 )

C C Symmetric stretch
C C Symmetric stretch
Methyl to chain rock

1524
1157
1004

Figure 1. Experimental set-up.

Figure 2. All-trans--carotene.

sample cell the third beam was reflected from the corner-cube
retroreflectors mounted on the computer-controlled translational stages (Physik Instrumente). Beams 1 and 2 are coming
simultaneously to the sample, whereas beam 3 is delayed.
All the three beams, arranged in a folded BOXCARS
configuration, are focused into the sample cell with the
help of a concave mirror, f = 300 mm. Owing to the folded
BOXCARS configuration, the FWM signal propagates in
a direction that diverges from that of the incoming beams
and can be easily separated by a pinhole. The signal is
recollimated by a lens, and led through a long path (8 m) that
should reduce the stray light from the cell windows. Finally,
the signal is dispersed by a 30 cm focal length monochromator
(Acton 302) and detected by a sensitive electrically cooled
CCD camera (Andor iStar).
In the case where the shaping of the pulses was
performed, beams 1 and 2 were passed through the phase
only pulse shaper, whereas beam 3, the probe beam, remained
unshaped. The pulse shaper consists of a pair of the
gratings, cylindrical mirrors and a liquid crystal mask in a 4f
arrangement.
The autocorrelation measurement of the pulse length
was performed by an autocorrelator (NOPA Pal) utilizing
second harmonic generation in a 0.05 mm thick BBO crystal.
The sample cell with a 300 m optical path contained the
all-trans--carotene dissolved in cyclohexane.

Figure 3. DFWM signal spectrum versus time delay.

Figure 4. Upper panel: fast oscillating DFWM transient. Lower

panel: sliding window FFT of the transient.

vibrational levels of the mode [6]. In the time domain, that

calls for a short pulse duration compared with the vibrational
period.
When unshaped, Fourier-limited, input pulses are
employed, several vibrational modes in the ground electronic
state are simultaneously excited. The typical transient in 2D
(signal spectrum versus time delay) is shown in figure 3.
The peak at time zero is called a coherence spike and
it is generated by diffraction of the probe beam from the
grating formed by the first two beams when all three beams
come simultaneously. After the coherence spike, the transient
shows dynamics that consist of several contributions, the
solvation dynamics, solventdye interaction and vibrational
wavepacket motion. The fast oscillations in the signal are
superimposed on long time dynamics and can be obtained by
taking a cut at the single wavelength from the 2D signal. These

3. Results
The first experiment presented here shows the time-resolved
DFWM signal with Fourier-limited pulses [4]. The structure
of the all-trans--carotene is shown in figure 2. The molecule
exhibits several vibrational modes and the most prominent
high-frequency modes and their origin is given in table 1.
In order to excite the vibrational wavepacket with fs
DFWM, the bandwidth of the pulse should cover two or more
2

Phys. Scr. T135 (2009) 014037

H Skenderovic

case with the unshaped pulses are shown in figure 5. The

uppermost trace shows that in the unshaped case, all of the
modes are present. The lower three traces show selective
excitation when the mask phase function was set for 1524,
1157 and 1004 modes, respectively.
The central wavelength of the laser also plays an
important role in the selective excitation of the vibrational
wavepackets in the ground electronic state. Two possible cases
exist: when the laser wavelength is resonant with the transition
from the electronic ground state to the excited state and when
the laser wavelength is out of resonance. Selective excitation
is possible in both cases, but it turns out [4] that in the resonant
case the enhancement of the selected mode is achieved.
Recently, density matrix simulations were reported [9]
that confirm the resonant enhancement in transient
absorption.

4. Conclusion
Figure 5. FFT spectrum for the transients excited with unshaped
pulses (upper trace), and FFT spectra for the excitation with shaped
pulses that match 1524, 1157 and 1004 cm1 modes, respectively
(lower three traces).

We showed that the DFWM with sub-20 fs pulses can

be applied for efficient excitation of the high-frequency
vibrational modes in a large molecule. Selective excitation of
the single mode is also demonstrated by shaped pulses. This
selectivity opens the opportunity to study the role of particular
vibrational modes in various photochemical reactions.

oscillations, shown in the upper panel of the figure 4, originate

from the vibrational wavepacket motion. Applying the sliding
window fast Fourier transform (FFT) analysis, the frequencies
contributing to the signal and their time development are
extracted; see the lower panel of figure 4. As the sliding
window FFT analyses show, all the three modes from table 1
are clearly visible in the signal with lifetimes of the order
of a picosecond. An additional frequency, at about 800 cm1 ,
originates from the cyclohexane vibrational mode.
In the second experiment, the pulse shaping of the first
two beams was applied in order to excite just a single
vibrational mode. As it is well known, periodic spectral phase
modulation leads to the generation of pulse trains [7, 8].
The temporal distance between subpulses in the pulse train
is determined by the spectral phase modulation frequency.
We applied a sinusoidal spectral phase modulation across the
mask for creating the subpulses. For a single vibrational mode
excitation the temporal distance between subpulses was set
to match the integer multiple of the period of the desired
vibration. The vibrational periods of the high-frequency
modes are in the 2030 fs range, and from the original
17 fs pulse it is not possible to construct the pulse train
with temporal separation exactly equal to the one of the
periods. However, the selective excitation is also efficient
when the temporal separation equals an integer multiple of
the period [4, 7].
The Fourier transforms of the transients obtained by
applying shaped pulses and the Fourier transform in the

Acknowledgments
I thank M Motzkus, J Hauer and T Hornung for their
invaluable contribution to this work. The Ministry of Science
Education and Sports of the Republic of Croatia (Project
No. 035-0352851-2857) and the Alexander von Humboldt
Foundation are gratefully acknowledged for financial
support.

References
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1990 Science 247 1317
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[7] Meshulach D and Silberberg Y 1998 Nature 396 239
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