Local Field Induced Four-wave Mixing with Third

Harmonic in Atomic System

Introduction
Time-resolved measurements with ultrashort pulses offers a wide variety of possible
experiments in optical spectroscopy.
Wave packets (WP) result from the coherent superposition of two or more eigenstates
in atoms or molecules and can be generated with pulsed lasers which are spectrally
broad and temporary short. Monitoring of the wave packets created from high-lying
atomic or molecular states in gas phase usually involves photoionization and detection
of ions or electrons created from pump-probe type measurements.
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The two-photon near resonant excitation of the upper states in potassium and
rubidium (eden, Felinto) generated WP which are monitored by quantum beating in
the intensities of the radiation created by FWM.
Atomic systems shined by intense fs laser pulses were frequently employed for the
third-harmonic [boyd, degert, vaicaitis] resonantly enhanced generation.
In this work we show how various wave-mixing phenomena combined in
pump/probe technique and phase-matched geometry can be utilised for creation and
monitor of the WP in all-optical type of measurements.

Fig 0. Picture of outgoing radiation after the interaction of three input beams with
sodium atoms
Sending three intense fs laser beams in usual folded box cars configuration into the
sodium vapor generates multitude of new beams at input near-IR wavelength
and third harmonic uv wavelength as can be seen in Fig.0. Quantum beating in
uv is observed by scanning time delay between input beams....
Experiment
In the experiment sodium vapor is produced in a standard linear heat-pipe
oven (HPO) fitted with fused silica windows and filled with sodium metal and helium
as a buffer gas.
The laser system is based on a mode-locked Ti:sapphire laser (Tsunami)
whose weak output at the repetition rate of about 80 MHz is amplified in chirpedpulse regenerative amplifier (Spitfire) which delivers approximately 700 J pulses at
1 kHz repetition rate. The output wavelength can be tuned from 760 to 860 nm. The
beam is split into three beams, 1, 2, and 3. On the way to the HPO the beams were
reflected from the corner-cube retroreflectors mounted on the computer-controlled
translational stages (Physik Instrumente). In this way, the desired temporal separation
between the beams is set. In the presented experiments the beams 1 and 2 are coming
simultaneously to the sample, while the beam 3 is delayed.
All the three beams, arranged in a folded BOXCARS configuration are
focused into the center of the HPO with the help of a concave mirror, f=500 mm.
Owing to the folded BOXCARS configuration, the FWM signal propagates in a
direction which diverges from that of the incoming beams and can be easily separated
by a pinhole. The signal is recollimated by a fused silica lens.

Results
The time-resolved Four-wave Mixing (FWM) spectroscopy can be utilized for
probing the three-level system consisting of one ground, g, and two closely spaced
excited states, e and f,

In the transient grating configuration the pulses from the beam 1 and 2 come
simultaneously in the focus and the pulse from beam 3 is delayed. At negative time
delays pulse 3 come before 1&2, and at positive delays pulse 3 comes after 1&2.
The signal at negative times shows dynamics of the excited states while the
signal at positive times can be both from the excited and ground states, as illustrated
by Feynman diagrams in Fig.1. The state vector a in the Fig. 1 corresponds to
ground state, g, and the state vector b represents either e or f excited states.

Fig 1 Upper row: Feynman diagram for negative delays. Lower row: Diagrams for
positive times, the first one representing time development of the excited state the
second and third development of the ground state.
Moreover, since the interaction at negative delay create coherence states eg
and fg, the time development of the signal should reflect the T 2 dynamics at the longtime scale. Also, an oscillatory pattern in the FWM signal could be present which
shows the beating between the fast oscillations of the time dependant wave functions
of f and e states. The interaction at positive time generates population ee or ff in the
excited states but also ef coherence. Therefore, the signal decays with T1 or T2 time,
whatever is shorter. In realistic systems where the interaction with the bath is
included, T2 is usually much shorter.
Our experiment is different from the ones usually studied in the resonant
FWM in a way that the excited states e and f are not one-photon but three-photon

resonant with the input beams. So that each wawy arrow in Fig. 1 corresponds to
interaction with three electric fields from the same beam. In this experiment we sent
the near infrared light with three beams which resulted in emission of ultraviolet light
as a signal in the fourth beam. Actually, it is a ten wave mixing process but in usual
FWM folded box-cars arrangement.
The system is sodium atom, and in two separate experiments two different
input wavelengths were employed for probing excited states. In the first experiment
the laser light is tuned to 804 nm which is resonant with the three-photon allowed
transitions to the two excited states, 6p1/2 and 6p3/2. as depicted in Fig. 2a. The onephoton transition from these states to the ground state is at 268 nm. The fine structure
splitting of the 6p doublet is 2.4 cm-1 so that both 6p levels can be excited by the laser
pulse.

Fig. 2 (a) Term diagram of sodium atom and the three-photon absorption at 804 nm.
and (b) at 865 nm.
The second experiment was done with the laser tuned to 865 nm which is
three-photon resonant with the 5p1/2 and 5p3/2 states (Fig. 2b). The radiation to the
ground state from these states is at 285 nm.
Similar results in TG measurements for both input wavelengths were obtained.
The time resolved TG signal at 268 nm is shown in the Fig. 3a. Time delay of the
third beam was scanned from -100 ps to +30 ps. At negative times nice oscillations
with amplitude can be seen. The period of the oscillation matches the energy gap
between the fine structure of 6p states. The amplitude of the beatings rises from the
large negative delays to the zero time delay where the signal abruptly falls.

The same pattern is seen at 285 nm when the laser output was tuned to 5p
three-photon absorption, Fig. 3b. Here, the oscillations are faster because of the larger
fine-structure splitting.

0,20

0,30

0,15

FWM Signal

FWM Signal

0,25
0,20
0,15
0,10
0,05

0,10

0,05

0,00

0,00
-100

-50
Time Delay (ps)

50

-80 -70 -60 -50 -40 -30 -20 -10

10

20

30

40

Time delay (ps)

Fig. 3 Time resolved transient grating signal at (a) 268 nm and (b) 286 nm.
The striking absence of the signal for the positive time delays is not expected
in TG measurements in gas phase. Quite opposite results can be found in other work
in literature when resonant fs FWM was applied. Beatings between upper resonant
levels is usually present both for positive and negative delays.
With the same FWM setup and the same HPO we looked the FWM signal
from the potassium resonant levels. It is known that in natural sodium there is a small
amount of potassium which is also present in the vapor phase as a trace element. By
tuning the laser beam at 769 nm (the middle between K resonant lines at 768 and 770
nm) we excited the first resonant levels, 4p 1/2 and 4p3/2. The time resolved FWM
showed beating between these two levels both for positive and negative times, as
expected.
The lack of the signal for positive delays in the main experiment can be
explained by the same mechanism which is involved in the long-known effect of the
decrease in ionization signal at the three-photon resonance from the frequency domain
spectroscopy...