FWHM Wit Fs Pulses

Coherent Control by Four-Wave Mixing
Hrvoje Skenderovi
Institute of Physics, Zagreb Graz, May 2008.
1
Coherent Control Introduction
Four-wave Mixing
-Carotene
Experiment
Control of Vibrational Modes
2
Motivation for the fs FWM spectroscopy
Fs FWM enables excitation and monitoring:
In gas, liquid and solid state

Excited and ground states
Rotational, Vibrational and Electronic states
Determination od spectroscopic constants with high precision

Ultrafast thermometry in extreme consitions (large pressure,
large temperature)
Real-time chemistry dynamics: Femtochemistry
Control and monitoring of molecular dynamics with shaped
pulses.
K. Nelson, A. Weiner, Fleming, Kiefer, ..., Motzkus 3

Coherent Control Four-Wave Mixing
The Four Wave Mixing (FWM) signal results from the polarization of the
sample following three consecutive electric field interaction.
ka
k1
k3

k2 k2
k3
k1
L
4
k3
k2
k S k1 k 2 k 3
ks
k1
Momentum and
Energy conservation
2 3
S 1 2 3 1 s
5
Time-resolved FWM experiments were done in

the following configuration:
Temporal Transient Grating
Geometrical Folded Box-Car
Laser Frequencies Degenerate
6
Boxcar configuration
ks
signal
k1
k2
k3
We look for the signal in the direction: ks = k1 k2 + k3
7
8
9
Transient grating: Two pulses come simultaneosly

The third is scanned in time
FWM TRANSIENT
Time Time
10
Optical Parametric Generation

Noncollinear optical Amplifier
White Light Generation NOPA (J. Yvon, A.G. Riedle)
Second Harmonic Generation 17 20 fs

11
Experimental Setup
1 2 3
NOPA;
490 nm,
17 fs
Linear
Stage
Pulse
Shaper
Time
Spectrograph Sample
3
Spherical Mirror
2
1
12
Coherent Control -Carotene
All-trans--Carotene ( N=11 )
Ground State Freq.(cm-1)

Vibrations
C=C Symmetric
stretch
1524
C-H Plane
bending
1269
C-C Symmetric
stretch
1157
Methyl to chain
rock
1004
13
Coherent Control -Carotene
FWM in -Carotene
Non-resonant Resonant
Sn Sn
S2 S2
S1 S1
DFWM 1,0 1,0
Absorption spectrum of
DFWM 500 nm
555 nm
Carotene
S0 S0
0,5 0,5
0,0 0,0
Hornung T. Skenderovi H. Motzkus M. 350 400 450 500 550 600 650
Observation of all-trans-beta-carotene wavepacket motion on the electronic ground and (nm)
excited dark state using degenerate four-wave mixing (DFWM) and pump-DFWM,
Chemical Physics Letters. 402(4-6):283-288, 2005 Feb 4. 14
Coherent Control Experiment
The first two pulses generate wave packets in the

ground and excited state via Impulsive Raman
1 2 3 a scattering.
e
Propagation of the packets is monitored by the
third pulse.
Observation of real-time vibrations requires that

the frequency bandwidth of the laser pulses
g overlap two or more vibrational levels.
Beside vibrational, other dynamics are present.

Rotational, restoration of solvent configuration,
etc...
15

2
I FWM ( ) P (t , ) dt
(3)
Calculation of the induced Polarization requires knowledge of the

third order density operator r(3)(t). The form of r(3)(t) follows from a
perurbative solution of the Liouville equation that describes evolution
of the system under the influence of the incident laser fields and
intrisic relaxation.
16
2D Transient 1D Transient
540
530
Wavelength (nm)
520
510
500
490
480
470
0 100 200 300 400 500 600
Time Delay (fs)
Vibrational dynamics
FWM Signal
600 900 1200
0 1000 2000 3000 4000 5000 6000 7000

Time Delay (fs)
17
Transient, nonresonant excitation, and sliding window spectrogram
18
Transient, resonant excitation, and sliding window spectrogram
19
Coherent Control Shaping
Coherent Control
Can we selectively excite just one mode employing pulse shaping?
0,0006
0,0005 1155.6
797.5
FFT Spectrum
0,0004
0,0003
1529.9
1009.1
0,0002
0,0001
0,0000
0 500 1000 1500 2000
-1
Frequency (cm )
20
0,4
Recipe
n T0
Shape the Pulse into several 0,3
replicas. Make the separation

between replicas equal to n T0 0,2
(T0 is vibrational period of the

mode to be excited) 0,1
[ M. M. Wefers, K. A. Nelson,
J. Opt. Soc. Am. B 12, 1342 (1995) ]
0,0
-400 -300 -200 -100 0 100 200 300 400
(fs)
Energy T(fs) 2 T(fs) 3 T(fs) 4 T(fs) 5 T(fs)

(cm-1)
1524 21.9 43.8 65.7 87.6 109.5
1157 28.8 57.6 86.4 115.2 144
1004 33.2 66.4 99.6 21

Third order polarisation, [Silberger et al, J.Chem. Phys. 118 9208 (2003)]
1
P (3) ( ) C d E3 ( ) A()
R i R
Two Photon Absorption: A() d ' E2* ( ') E1 ( ')
1,0
p=20 fs
0,8
p=15 fs
0,6

A()
0,4
0,2
0,0
0 500 1000 1500 2000
-1 22
(cm )
How to select R : Frequency domain approach
A( R ) d ' E2* ( ') E1 ( R ') E() E() ei( )
( ) (R ) 0 Phase should be
Konstructive Interference at R for every periodic with R
Destructive Interference for other

0,08 ( ) a sin 2 N c
R
-1
Pulse Train for 1004 cm
0,07
FL Pulse
0,06
0,05
A()
0,04
0,03
0,02
0,01
0,00
0 500 1000 1500 2000
-1 23
(cm )
620
600
Wavelength (nm)
580
560
540
520
500
-200 -100 0 100 200
Time (fs)
1524
1157
1004
0 500 1000 1500 2000

-1
wavenumber (cm ) 24
Non-resonant case, conclusions
Non resonant DFWM with ultrashort pulses

efficiently excites high-frequency vibrational modes
in ground state with pulse replicas set at N * T
Selective excitation with shaped pulses is achieved
Can we increase the selective excitation efficiency
with resonant DFWM?
25
DFWM - Resonant case
Sn
S2
S1
DFWM
500 nm
S0
Hauer J. Skenderovi H. Kompa K-L. Motzkus M.

Enhancement of Raman Modes by Coherent Control in -Carotene.
Chem. Phys. Lett. 421 523-528 (2006).
Hauer J. Buckup T. Skenderovi H. Kompa K.-L. Motzkus, M.Selective
preparation of vibrational states in complex molecules by quantum control //
Quantum Computing: Back Action, Kanpur, India 2006..
26
27
n
S (t ) i sin( i t i )
A e
i 1
t / i
/ fs
1,0
EXP
FIT
0,5 1004 1200

DFWM Signal
1156 1350
0,0
1532 650
-0,5
1390 144
800 900 1000 1100 1200
(ps)
28
Applying multipulse sequences matching the periodicity of single

vibrations, the modes of b-carotene solvated in cylcohexane were
not only specifically excited, but under resonant conditions also
enhanced compared to the Fourier-limited case.
This effect is attributed to an increased population transfer to the
excited state and stronger coherences created and demonstrates
the feasibility to selectively amplify ground state Raman modes by
coherent control.
29
At 484 nm At 538 nm
0,45
0,35
0,30
5,7 Shaped 0,40
0,35
1,8
0,25
0,20
Unshaped 0,30
0,25
0,20
0,15 0,15
0,10 0,10
0,05
0,05
0,00
0,00
800 1000 1157 1524
800 1000 1157 1524
0,50
0,50
0,45
0,45 1,3
0,40 5,5 0,40
0,35
0,35
0,30
0,30
0,25
0,25
0,20
0,20
0,15
0,15
0,10
0,10
0,05
0,05
0,00
0,00
1000 1000 1157 1524

1157 1524
0,15 2,5 0,45

0,40 1,2
0,10 0,35
0,30
0,25
0,05 0,20
0,15
0,10
0,00
0,05
1000 1157 1524 0,00 30
1000 1157 1524
Absorption spectrum of 1,0 1,0
Carotene
0,5 0,5
0,0 0,0
450 500 550

(nm)
31
[] we conclude that the physical mechanism

responsible for increasing/suppressing of the S0 S1
population transfer is resonant excitation of
the underlying vibrational states
by keeping them in a coherent superposition during
the excitation.
[N. A. Prokhorenko VI, Miller RJD, JOURNAL OF CHEMICAL PHYSICS 122,

Art. No. 184502 (MAY 8 2005, 2005)]
32
Theory of resonant DFWM
Buckup T. Hauer J. Serrat C. Motzkus M. Control of excited-state population

and vibrational coherence with shaped-resonant and near-resonant excitation
Journal of Physics B-Atomic Molecular & Optical Physics. 41(7):74024, 2008 Apr 14.
33
Acknowledgment
Max-Planck-Institut fr Quantenoptik, D-85748 Garching

Institute of Physics, HR-10001, Zagreb
J. Hauer
T. Hornung
M. Motzkus K. L. Kompa
G. Pichler
34
Third Harmonic Generation in Na IFS
Third harmonic generation in sodium

by Parametric Wave Mixing PWM
35
Two beams, angular phase-matching,

enhancement of THG
36
N
(3 )
(3)
3
mn
g n nm mg
1

( g 3 )(ng 2 )(mg )
1

( g )(ng 2 )(mg )
1

( g )(ng 2 )(mg )
1

( g )(ng 2 )(mg 3 )
37
38
Third beam - Mode competition
Time
39
40
Dr. Goran Pichler

Dr. Ticijana Ban
Dr. Damir Aumiler
Silvije Vdovic
Natasa Vujicic
H.S.
41
Thank you
42

FWHM Wit Fs Pulses

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

FWHM Wit Fs Pulses

Uploaded by

Copyright:

Available Formats

Coherent Control by Four-Wave Mixing

Motivation for the fs FWM spectroscopy

Fs FWM enables excitation and monitoring:

In gas, liquid and solid state

Determination od spectroscopic constants with high precision

K. Nelson, A. Weiner, Fleming, Kiefer, ..., Motzkus 3

Time-resolved FWM experiments were done in

Temporal Transient Grating

Geometrical Folded Box-Car

Laser Frequencies Degenerate

We look for the signal in the direction: ks = k1 k2 + k3

Transient grating: Two pulses come simultaneosly

Optical Parametric Generation

Second Harmonic Generation 17 20 fs

Ground State Freq.(cm-1)

The first two pulses generate wave packets in the

Observation of real-time vibrations requires that

Beside vibrational, other dynamics are present.

Calculation of the induced Polarization requires knowledge of the

600 900 1200

0 1000 2000 3000 4000 5000 6000 7000

Transient, nonresonant excitation, and sliding window spectrogram

Shape the Pulse into several 0,3

replicas. Make the separation

(T0 is vibrational period of the

Energy T(fs) 2 T(fs) 3 T(fs) 4 T(fs) 5 T(fs)

1524 21.9 43.8 65.7 87.6 109.5

1157 28.8 57.6 86.4 115.2 144

1004 33.2 66.4 99.6 21

Two Photon Absorption: A() d ' E2* ( ') E1 ( ')

How to select R : Frequency domain approach

A( R ) d ' E2* ( ') E1 ( R ') E() E() ei( )

Destructive Interference for other

0 500 1000 1500 2000

Non-resonant case, conclusions

Non resonant DFWM with ultrashort pulses

DFWM - Resonant case

Hauer J. Skenderovi H. Kompa K-L. Motzkus M.

0,5 1004 1200

Applying multipulse sequences matching the periodicity of single

1000 1000 1157 1524

0,15 2,5 0,45

Absorption spectrum of 1,0 1,0

450 500 550

[] we conclude that the physical mechanism

[N. A. Prokhorenko VI, Miller RJD, JOURNAL OF CHEMICAL PHYSICS 122,

Theory of resonant DFWM

Buckup T. Hauer J. Serrat C. Motzkus M. Control of excited-state population

Max-Planck-Institut fr Quantenoptik, D-85748 Garching

Third harmonic generation in sodium

Two beams, angular phase-matching,

Third beam - Mode competition

Dr. Goran Pichler

You might also like