ultrafast electronic spectroscopy.ppt...bacteriorhodopsin isom. ≈ 70 % in protein isom. ≈ 17 %...
TRANSCRIPT
![Page 1: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/1.jpg)
Ultrafast electronic spectroscopy
Majed Chergui
![Page 2: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/2.jpg)
Arrhenius formulaTkE BaAeTk /)( in sec-1
A = frequency factorkB = Boltzmann constantT = temperature (in Kelvin)Ea= activation energy
A ~ 1013 !*Kinetics: overall population of reactantsbefore the reaction and of products afterthe reaction
* Note that this corresponds to times of the order of 100 fs
![Page 3: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/3.jpg)
The fundamental time scale in Condensed Matter, Chemistry and Biology
• Speed of sound: 300 m/s-1000m/s => 0.3-1.0 Å in 100 fs
• Time scale of half-oscillations:H2; e= 4155 cm-1 —> 7.6 fsI2; e= 120 cm-1 —> 270 fs
• 1fs / 1s <=> 1s / 32 million years!
![Page 4: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/4.jpg)
Vibrational period of H2 in the X state (e = 4401 cm-1) 7.6 fs
Rotational period of H2 in the X state (EJ = 2BJ, B = 60cm-1):
560 /J fs
Vibrational period of I2 in the B state (e = 125 cm-1) 270 fs
Rotational period of I2 in the B state (EJ = 2BJ, B = 0.029 cm-1): 1.15 /J ns
Vibrational period of a van der Waals molecule Hg-Ar in the Xstate (e = 6 cm-1)
6 ps
Rotational period of Hg-Ar in the B state (EJ = 2BJ, B = 0.02cm-1)
800 /J ps
Number of periods in a 6fs-pulse at 600 nm 3
Length of a 6fs-laser pulse 1.8 m
Spectral width of a 1 ps pulse 15 cm-1
![Page 5: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/5.jpg)
Conventional spectroscopy (energy resolved)also called CW (continuous wave) or steady-state spectroscopy
![Page 6: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/6.jpg)
Time-wavelength relationship
![Page 7: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/7.jpg)
Correspondence between energy and time
• Doppler width 10-3 to 10-1 cm-1
• Rotational energies 10-2 to 10 cm-1
• Phonon energies ≤ 100 cm-1
• Vibrational energies 100 to 4000 cm-1
• Electronic energies ≥ 5000 cm-1
Time-to-width relationships for homogeneous lines
Energy (cm-1 ) Time (seconds)500 10-14
5 10-12
5 10-4 10-8
![Page 8: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/8.jpg)
For a molecular state (e.g. diatomic molecule)
Left: Decay of the autocorrelation function. Right: absorption spectrumT: time to depart from the Franck-Condon regionT: oscillation period of a vibrational quantum in the excited stateT3: electronic lifetime of the state
![Page 9: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/9.jpg)
Decay of H2O, qualitative picture: saddle-shaped potential surface
Bending motion
YX…Y elongation
![Page 10: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/10.jpg)
Photodissociation of H2O
Absorption spectrum
Time evolution of the autocorrelation function
![Page 11: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/11.jpg)
Resonance Raman: time dependent view
![Page 12: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/12.jpg)
Resonance Raman spectrum of CH3I
Exc. 266 nm
mre et al, JPC 84
![Page 13: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/13.jpg)
Some basic quantum mechanics…The time-dependent Schrödinger equation:
has solutions of the form
where (r) is the eigenfunction, which is the solution of the time-independent Schrödinger equation and the exponential term represents the time dependence.
ttritrH
),(),(
/)(),( iEtertr
![Page 14: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/14.jpg)
Superposition of states
n
nn rar )()0,(
)/sin()/cos(/ EtiEte iEt
oscillates from 1 to –i to 1 to i …, at a frequency of /E
e.g., the 2s state has an energy of E= 1.6 10-18 J, i.e. the phase oscillatesat 2.5 1015 Hz (i.e. T= 0.4 fs)
![Page 15: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/15.jpg)
• This is a linear combination of stationary wave functions but is not a solution of the stationary problem. It represents a coherent superposition of states or a wave packet. The an coefficients are given by:
)0( ta nn
/)(),( tiE
nnn
neratr
![Page 16: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/16.jpg)
ˆ t t t
ˆ ˆ,t Hdidt
ˆ ˆ ˆˆ ˆ( )j
A A ATr j j
2
jj jc * jk jki t i tjk j k jkt c c e d e
Density matrix description in Liouville space
![Page 17: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/17.jpg)
Wave packets
![Page 18: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/18.jpg)
Vibrational wave packets
![Page 19: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/19.jpg)
Forms of ultrafast temporal evolution of excited states
• Kinetics: exponential behaviour, evolution of populations
• Dynamics: oscillatory behaviour (wp), evolution of bodies
![Page 20: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/20.jpg)
How to create a wavepacket?
![Page 21: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/21.jpg)
How to create a wavepacket?
(r , t ) an n (r)e iE n t /
n
k
k dktrkgtr ),()(),(
![Page 22: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/22.jpg)
![Page 23: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/23.jpg)
Pump-probe and wavepacket dynamics
0 1 2 3
1
2
3
retard pompe - sonde / picosecondes
t = 300 fs
Pump-probe time delay
![Page 24: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/24.jpg)
3 �m �� 10fs
![Page 25: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/25.jpg)
QuickTime™ and a decompressor
are needed to see this picture.
3 �m �� 10fs
![Page 26: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/26.jpg)
Possible experimental strategies• Transient absorption
Pump-Probe spectroscopy• TR fluorescence
• Non-linear Four WaveMixing spectroscopies– Transient Grating– Photon Echo
• X-rays techniques
• Multidimensionalspectroscopies
• Terahertz spectroscopy...
![Page 27: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/27.jpg)
![Page 28: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/28.jpg)
Revivals: S.I. Vetchinkin et al, Chem. Phys. Letters, 222 (1994) 394
![Page 29: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/29.jpg)
Zewail et al, J. Phys. Chem. 1996, 100, 7832-7848
![Page 30: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/30.jpg)
Transfer of vibrational coherence to products (Zewail et al, J. Chem. Phys. 91 (1989) 7437)
![Page 31: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/31.jpg)
Transfer of coherence to products in a bath(Banin and Ruhman, J. Chem. Phys. 98 (1993) 4391; Pugliano et al, J.
Chem. Phys. 104 (1995) 5062)
IInmhI 23 )308(Solute/pump-fragment/probe experiment:
I2-
![Page 32: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/32.jpg)
Vibrational wave packets (moving structures) in biological systems using transient absorption spectroscopy
![Page 33: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/33.jpg)
From L. Stryer, Biochemistry
Retinal Proteins
11-cis all-trans
13-trans 13-cis
Rhodopsin
Bacteriorhodopsin
Isom. ≈ 70 % in proteinIsom. ≈ 17 % in solution
![Page 34: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/34.jpg)
![Page 35: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/35.jpg)
poche
Heme
Heme pocket
Fe C O
![Page 36: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/36.jpg)
The inset show the absorption band and the pump and probe wavelengths.The figure shows the transient absorption signal of deoxy Mb
The lower figure is a comparison of the power spectrum of the transient in the upper figure with the resonance Raman spectrum of deoxy Mb
![Page 37: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/37.jpg)
Transient absorption spectrum of MbNO. The inset show the absorption bands of Mb and MbNO.
Power spectrum of the trace in The upper figure and resonanceRaman spectrum of MbNO.
Rosca et al, J. Phys. Chem. A104 (2000) 4280)
![Page 38: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/38.jpg)
Summary• Vibrational coherences are observed in a large
class of many-body systems: large molecules, liquids, solids, proteins, etc., even upon product formation.
• Energy can be localised on specific intra- and intermolecular bonds, for eventual control experiments.
• While for chemical and physical systems, the connection between the process and the vibrational coherences is possible, vibrational coherences in proteins do not necessarily imply that the motion that is observed is biologically significant.
![Page 39: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/39.jpg)
Ultrafast emission spectroscopy
• electronic (ps-ns)– TC-SPC – Streak Camera
• purely optical (sub-ps)– Kerr Gating– Up-conversion
![Page 40: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/40.jpg)
Fluorescence Gating
Time delay between pump and gate pulses
I
![Page 41: Ultrafast electronic spectroscopy.ppt...Bacteriorhodopsin Isom. ≈ 70 % in protein Isom. ≈ 17 % in solution poche Heme Heme pocket Fe C O The inset show the absorption](https://reader033.vdocuments.us/reader033/viewer/2022060821/6099da5e69d57569097ad503/html5/thumbnails/41.jpg)
Fluorescence Up-conversion