16/04/2007 1

Time-resolved
Spectroscopy
A. Yartsev
16/04/2007 2
Important Factors for Time-
resolved Spectroscopy.
Temporal resolution pulse duration.
Spectral resolution bandwidth and
tunability.
Efficient start of the dynamics of interest
high intensity of Pump pulse.
Fast process to probe the dynamics
tunability and intensity of Probe pulse.
Sensitive detection.
Data analysis and modelling.
16/04/2007 3
Direct Temporal Resolution
Absorption: Flash-photolysis fast detector
and fast oscilloscope.
Fluorescence: Time-Correlated Single
Photon Counting (TCSPC).
STREAK camera.

16/04/2007 4
Pump-Probe Correlated
Temporal Resolution.
Strong Pump weak Probe
Transient absorption
Transient gaiting
Strong Pump strong Probe
Multiphoton ionization
Integrated fluorescence
RAMAN etc.
Strong Pump strong Gate
Fluorescence up-conversion
Optical Kerr Effect
Coherent methods
16/04/2007 5
Temporal Resolution From
Data Analysis.
Sub-instrumental response dynamics
Fluorescence phase-shift method
Excitation correlation fluorescence
Coherent: 3PEPS
16/04/2007 6
Spectral Resolution.
Uncertainty principle limitation:
short time needs broad spectrum!
Tunability of the pump and probe
light is available through various
lasers, frequency conversion and
fs-continuum.
Spectral sensitivity of detector.
Is the uncertainty principle applied for
detection as well?
16/04/2007 7
Short Pump Pulses.
Fast excitation temporally clean
start of process.
High intensity of the light non-linear
effects can be used for excitation and
probing.

16/04/2007 8
Problems with Short Pump Pulses.

Broad spectrum lack of spectral
selectivity.
Non-linearity may induce complications in
the dynamics of interest.
Artefacts: - may complicate early time
scale dynamics.
16/04/2007 9
Short Probe Pulses.
Make fine grid to accuratelly resolve the
dynamics.
Short probe pulse + fine time grid
accurately resolved dynamics.
Broad probe spectrum is good to
resolve new transitions.
16/04/2007 10
Problems with Short Probe Pulses.

Broad spectrum lack of spectral selectivity.
Non-linearity may the probe-induced dynamics.
Artefacts: - spectrally non-even detection
efficiency may lead to XFM.
16/04/2007 11
What can we get from absorption?
Absorption spectrum as a fingerprint of a molecule.
From absorption, path length and Beer-Lambert law:
Concentration c[mol*dm
-3
] from extinction c[dm
3
mol
-1
cm
-1
]
Or extinction c from concentration c.
Molecular cross-section o[cm
-2
] from C[cm
-3
].
transition dipole moment from spectral shape of c.

And with short pulses we can time-resolve this all!
16/04/2007 12
Time-resolved Absorption
Single colour
Shot to shot.
Lock-in technique: chopped pump or both pump
and probe are chopped at different frequencies
and the signal is measured at differential
frequency.
Pseudo two-colour.

Multiple colour
Single shot single
probe
: point-by-point.
Single shot whole spectrum.
16/04/2007 13
Differential absorption: weak Probe.
Lock-in technique: filter the Probe light noise out,
keep the Pump contribution only.
Differential absorption AA(t) as a difference in
transmission with- and without Pump.
Reference beam: bypassing or passing through
the sample?
Locked-in reference beam scheme.
16/04/2007 14
Lock-in Technique
Investigate the Probe beam fluctuations.
Modulating the Pump beam at a frequency in a
silent part of noise frequency spectrum.
Biuld a narrow frequency filter to transmit only the
frequency of Pump modulation.

16/04/2007 15
Differential absorption.
Differential absorption AA(t) (transmission AT(t)):
AA(t) = A(t) A*(t) = -Log(I*
out
/I*
in
) + Log(I
out
/I
in
)
How to convert AA(t) into AT(t)?
How to measure AA(t) with I
out
only?

If I
in

is stable (I
in
=

I*
in
): AA(t) = -Log(I
out
/I*
out
)

If I
in

is not stable (I
in
=

I*
in
) a reference I
ref
is needed:
AA(t) = -Log(I*
out
I
ref
/I*
ref
I
out
)

16/04/2007 16
Locked-in Refence Scheme.
When collecting large
number of shots for
averaging out the noise
each pair of pulses with-
and without- Pump is
treated separately.
The the long-time noise
is then filtered out.
16/04/2007 17
Polarized Light
Pump Probe: A

and Pump Probe: A

Magic Angle signal (MA) is sensitive to
population dynamics only
MA = (A

+ 2A

)/3
Why MA signal can be measured at
~54.7 between pump and probe?
And anisotropy signal r(t) is sensitive to dipole
orientation only
r(t) = (A

- A

)/(A

+ 2A

)
16/04/2007 18
Instrumental function and zero-time.
Often a very good time-resolution has to be
characterized at the spot.
Instrumental response is generally varied over the wide
probe spectrum.
Zero time position is crytical and often difficult to define.
Several options to characterize both:
SHG of Probe and Pump
Two-photon (one from Pump, one from Probe) absorption
Set of reference samples
OKE in samples with little nuclear response
16/04/2007 19
Un-correlated and Correlated
Noise.
Un-correlated (independent) noise when A

and
A

are measured after each other noise is of
two measurements is larger than for each of them.

A

and A

are measured simultaneously for each
laser pulse may be much smaller (if noise is
correlated).
Important: identical temporal- and spatial- overlap
with pump!
16/04/2007 20
Signal-to-Noise: detectors
Two types of noise: Probe and Pump.
Light level: how accurate one can count photons?
Integrated- or spectrally- resolved detection?
Dark noise and digitizing limitations of electronics.
Peak- or Integrating- detector?
Pump noise: normalization and spatial fluctuations.
Pump noise: one time-point many shots or many
time-points few shots?
Averaging... For how long?
16/04/2007 21
Dependence of the noise level
on Probe-pulse energy.
16/04/2007 22
-0.0005
-0.0004
-0.0003
-0.0002
-0.0001
0.0000
0.0001
300 350 400
Sweep 500ps
Sweep 22ps
Sweep 1ps
Scan 284
Scan 116

A
b
s
Time (ps)
Type of
experim
ent
Measur
ements
per
point

Number
of
repeats
Total
measur
ements
Number
of time
point
used
k1
(1/ps)
Uncer
tainty
1 %
k2
(1/ps)
Uncer
tainty
2 %

k3
(1/ps)
Uncer
tainty
3 %

Scan

300 12 3600 116 0.309 13.3

0.0348 89.8

0.0097
5
36.7

Scan

500 4 2000 284 0.327 13.2

0.0445 52.0

0.0097
7
13.6

Swee
p

1 100 100 5652 0.314 3.6

0.0365 16.1

0.0096
2
3.9

16/04/2007 23
How Strong Should Be Pump and
Probe Light?
Pump intensity: linear and non-linear signal.
Non-linear absorption: multi-photon absorption
and absorption saturation
Sequential (two-steps) absorption
Concentration-dependent dynamics.
Relative Pump/Probe intensity:
Strong Pump Weak Probe?
Probe intensity: how weak should be Probe?
16/04/2007 24
How weak should be Probe?
Additional A amplitude induced by Probe itself
has to be smaller than the noise level needed to
resolve Pump-induced changes.

Easily achievable out of absorption region.

In the absorption region: possible Probe self-
induced effect in differential absorption.
What should be the relative density of photons
to induce 10
-4
differential signal by Pump or by Probe itself?
Decrease Probe intensity by reducing number of
photons or by increasing beam diameter.
16/04/2007 25
Transient absorption:

Advantages:
Probe pulse is relatively easy to tune.
Even dark excited states can be seen
by S
1
S
n
absorption.

Gives total picture of the involved components.
Very good temporal resolution and signal-to-noise.
Disadvantage:
Sometimes too much information difficult to
interpret.
Good to combine with time-resolved fluorescence.
16/04/2007 26
Homodyne detection: transient grating.
In homodyne transient absorption (i.e. transient
grating or OKE) only the signal field is recorded.
I
det
|E
s
(t)|
2
AA(t) [R(t)*K(t)]
2

R(t) rotational correlation function,
K(t) populational decay function

In heterodyne scheme (i.e. Differential absorption)
additional light field (Local oscillator) is added.
I
det
|E
LO
+E
s
|
2
= I
s
+ I
LO
+ nc/4t Re[E*
LO
(t)E
s
(t)]
I
s
is realtively weak, I
LO
can be removed by chopping
detected signal is linearized against Pump.
16/04/2007 27
Time-resolved fluorescence.
Clear method: emissive excited state dynamics.

Isotropic decay: MA(t) = (I
par
+2I
per
)/3

Anisotropy decay: r(t) = (I
par
-I
per
)/(I
par
+2I
per
)

16/04/2007 28
Time-resolved fluorescence.
Direct, electronic resolution.
Fast photodiode (PMT) + fast oscilloscope.
Time-correlated single photon counting
STREAK camera

Inderect methods.
Fluorescence gaiting (up-conversion, etc.).
Excitation correlation method.
Phase-shift method.


16/04/2007 29
TCSPC
16/04/2007 30
TCSPC
Advantages:
High sensitivity
Statistical noise
Electronics-limited
Disadvantage: low time resolution: 20-30 ps
Sensitivity: (much less than) single photon level.
16/04/2007 31
Schematic of STREAK camera
16/04/2007 32
STREAK camera
Advantages:
Direct two-dimensional resolution.
Sensitivity down to single photon.
Very productive.
Disadvantage:
Depends on high stability of laser.
Limited time resolution: 2-10 ps.
Needs careful and frequent calibration.
Expensive.
16/04/2007 33
Up-conversion
Advantage: (very) high time resolution, limited
mainly by laser pulse duration.

Disadvantages:
Demanding in alignment.
Limited sensitivity, decreasing with increasing
time resolution (crystal thickness).
Required signal calibration.
J. Shah, IEEE J. Quant. Electr., 1988, 24, 276288.
M. A. Kahlow, W. Jarzeba, T. P. DuBruil and P. F. Barbara, Rev. Sci. Instr., 1988, 59, 1098
1109.
16/04/2007 34
Fluorescence up-conversion set-up.
L. Zhao, J. L. Perez Lustres, V. Farztdinov and N. P. Ernsting
Phys . Chem. Chem. Phys . , v. 7 , 1716 1725, 2005
16/04/2007 35
Broad-band up-conversion with
amplified short pulses.
Broad phase-matching
by type II crystal
Tilted gate pulses for
sub-100 fs resolution
Optimized scheme: ~ 1
count/channel per pulse

L. Zhao, J. L. Perez Lustres, V. Farztdinov and N. P. Ernsting
Phys . Chem. Chem. Phys . , v. 7 , 1716 1725, 2005
16/04/2007 36
Fluorescence Kerr gating
Advantages:
Complete spectra no phase matching
Good time resolution: 200-400 fs
Reasonable sensitivity
Disadvantage:
large background
Better resolution gives less signal
16/04/2007 37
S. Arzhantsev and M. Maroncelli
Applied Spectroscopy, V 59, N 2, 206-220, 2005

Kerr gating
16/04/2007 38
Strong Pump strong Probe
Pump-induced intermediate is selectivelly in time
and wavelength transfered into an easily
detectable state.
Multiphoton ionization: very sensitive and accurate
TOF detection
Pump-Probe induced fluorescence: measured by a
sensitive integrating detector (PMT).
Probe-induced RAMAN or CARS scattering.

16/04/2007 39
Time-resolved RAMAN and
CARS
Record changes in vibrations to
follow dynamics of the process.
Spontaneous scattering in RAMAN
is amplified in CARS: stronger and
spatially selected signals .
As CARS is strong and is often a
molecule-specific time-resolved
CARS of excited state can be used
as a sensitive probe tool.
16/04/2007 40
New twist of time-resolved
spectroscopy.
By a first pulse prepare a particular state;
By the second pulse induce some dynamics
in this state;
By a Probe pulse (strong or weak) resolve
the dynamics in this new state.

Pump-Dump-Probe;
Pump-Re-Pump-Probe
16/04/2007 41
Electro-induced differential
absorption
The signal reflects EF-induced changes in the
photoinduced dynamics.

EDA(t) = -Log(I
EF
out
I
ref
/I
EF
ref
I
out
)

In this way, one can study a dynamic effect of
EF not switching ON or OFF EF but rather by
timely injection of system of interest into EF



16/04/2007 42
Scheme of EDA
experiment
EF-generator
pump pulse
probe
pulse
to detector
SI from
LASER
16/04/2007 43
Optimal (Coherent) Control
This is another technique where the effect of
Pump is specially treated.
The shape of the Pump pulse is optimized so that
it has MAX influense on a particular process of
interest.
In such a way, a minor part of regular sample
response (for TL pulse) could be expressed and
become dominant.
16/04/2007 44
Pump - Shaped Dump Probe Scheme
probe
shaped dump
pump
delay time
sink region
cis trans

N
C
2
H
5
N
C
2
H
5
I
-
+



p
o
t
e
n
t
i
a
l

e
n
e
r
g
y
515 nm
630 nm
550 nm
16/04/2007 45
2
1
CI seem

i
n
t
e
n
s
i
t
y
delay time