Ultrafast Transient Absorption Spectroscopy

a practical introduction

Dr. Elisabet Romero

Dr Elisabet Romero
3rd June 2013
Manolis Papagiannakis
Overview of electronic/vibrational transitions
Why ultrafast?

• Molecular photodynamics occur on that scale

[energy transfer, internal conversion, vibrational
relaxation, etc.]
• Molecules move with respect to each other on a
time scale of 10 fs -1 ps (10-14-10-12s)
• Reactions
R ti which
hi h constitute
tit t the
th transfer
t f or
movement of a proton or electron or C-atons
occur on these
th ti
time scales.
l
Time-resolved absorption changes

follow the absorption changes after shining laser-light

The actual experiment
Excitation laser:
•Repetition rate
•Pulse
P l d duration
ti
•Emission wavelength
•Polarization
•Intensity
I t it (power,
( focusing,
f i etc)
t )
Sample:
•Biochemistry
•Buffer/solvent
•Concentration
•Cuvette ((material, p
pathlength)
g )
•Refreshing (pumping, moving, etc.)
•Temperature (RT, 77K)
Detection:
•One/multi-wavelength
•Diode array/ CCD
•Spectrograph/ grating
•Spectral region
Amplified laser systems

Time-bandwidth product: short means broad!

t 

B d means chirped!
Broad hi d!
B R

Chirped Pulse Amplification

Amplify from nJ to mJ
→ peak power = 1012W/cm-2
=103 times damageg threshold
of most materials!
oscillator stretcher amplifier compressor
Femtosecond spectrophotometer

NOPA

STRETCHER

COMPR
Ti:S
ESSOR

AMPLIFIER
Chopper
pp

Nd:Yag Nd:YLF

Laser system
sample

800 nm

400 nm
Tunable 2 DIODE-ARRAY DETECTOR
excitation MONOCHR .
Continuum
Dispersed pump-probe

time

pump
p p probe
p pump-probe
p pp
Absorbance changes

I ( ) pumpOFF
OD  OD( , t ) pumpON  OD( ) pumpOFF  log
I ( , t ) pumpON
sample
pump I

I
probe
∆OD
D

λ
 Time-resolved absorption changes monitor photodynamics

Excited
state
t t N

∆A)
nce difference (∆
ESA
Excited ESA
state 1
Energy


E

Stimulated
d

Stimulated
d

bsorban
emission

emission
pump

Ground

Ab
S

S
e

state
I ( ) pumpOFF
A  A( , t ) pumpON  A( ) pumpOFF  log
I ( , t ) pumpON
Reaction coordinate
The actual experiment
Excitation laser:
•Repetition rate
•Pulse
P l d duration
ti
•Emission wavelength
•Polarization
•Intensity
I t it (power,
( focusing,
f i etc)
t )
Sample:
•Biochemistry
•Buffer/solvent
•Concentration
•Cuvette ((material, p
pathlength)
g )
•Refreshing (pumping, moving, etc.)
•Temperature (RT, 77K)
Detection:
•One/multi-wavelength
•Diode array/ CCD
•Spectrograph/ grating
•Spectral region
Pump-probe data: Photosystem II Reaction Center
Pump-probe data: Photosystem II Reaction Center

-10

mOD / a.u.
-20

-30

-40
450 500 550 600 650 700
Wavelength / nm

0
2

-10
OD / a.u.

OD / a.u.
0
mO

mO
-20

-2
-30

-4 -40
450 500 550 600 650 700 660 680 700
Wavelength / nm Wavelength / nm
Global Analysis:
spectral
p evolution

500 fs 3 ps 20 ps 300 ps 600 ps 20 ns

2 0
u.
mOD / a.u

0 -10

mOD / a.u.
-2
-20
0

m
-4
450 500 550 600 650 700 -30
Wavelength / nm

-40
660 680 700
Wavelength / nm
Target Analysis: Kinetic scheme

2 0
mOD / a.u.

0 -10

a.u.
mOD / a
-2
-20

-4
450 500 550 600 650 700 -30
30
Wavelength / nm

-40
660 680 700
Wavelength / nm
Some concerns

• The repetition rate of laser must be slower than the photocycle

or relaxation of the molecules, otherwise, the sample must be
refreshed before every laser shot (e.g. by flowing)

• The excitation density y (p

(photons/time*area)) must be low,, only y
when less than 10% of complexes are excited is the measurement
in a linear regime. Otherwise effects as annihilation, saturation and
orientational saturation become important.
important

• Population dynamics are measured under the ‘magic’ angle

54 7°, at other angles orientational dynamics are measured!
54.7
Anisotropy: r = (∆DOD// -∆DOD) / (∆OD// + 2∆OD)