Attosecond Flashes of Light – Illuminating electronic quantum dynamics – XXIIIrd Heidelberg Graduate Days Lecture Series Thomas Pfeifer InterAtto Research Group MPI – Kernphysik, Heidelberg.
Download ReportTranscript Attosecond Flashes of Light – Illuminating electronic quantum dynamics – XXIIIrd Heidelberg Graduate Days Lecture Series Thomas Pfeifer InterAtto Research Group MPI – Kernphysik, Heidelberg.
Slide 1
Attosecond Flashes of Light
– Illuminating electronic quantum dynamics –
XXIIIrd Heidelberg Graduate Days
Lecture Series
Thomas Pfeifer
InterAtto Research Group
MPI – Kernphysik, Heidelberg
Slide 2
Contents Yesterday
Attosecond Pulses
Classical and quantum mechanics of electrons
- Classical Motion of Electrons
definition of important quantities
- Quantum Mechanics
· Electron dynamics in (intense) laser fields
· Ionization
- High-harmonic generation: quantum mechanical view
Slide 3
Contents
Basics of short pulses and general concepts
Attosecond pulse generation
Mechanics of Electrons
single electrons
in strong laser fields
Attosecond Experiments with isolated Atoms
Multi-Particle Systems
Molecules
multi-electron dynamics (correlation)
Attosecond experiments with molecules / multiple electrons
Ultrafast Quantum Control
of electrons, atoms, molecules
Novel Directions/Applications
Technology
Slide 4
High Harmonics Quantum Mechanical
M. Lewenstein et al. Phys. Rev. Lett. 49, 2117 (1994)
1
S ( p , t , t )
t
t
~
p eA( t )
2m
2
~
dt
Slide 5
high-harmonic generation
intense laser field acting on single atom
probability distribution p(x,y)=|Y(x,y)|2 for the electronic wavefunction
laser polarization
Slide 6
Wavepacket spreading
Slide 7
Split-Step Operator Technique
Slide 8
Streak field spectroscopy
quantum mechanically, with interference
Goulielmakis et al. (Krausz group), Science 305, 1267 (2004)
Slide 9
Streak-field spectroscopy
Drescher et al., Nature 419, 803 (2002)
Slide 10
Auger decay in Kr
Drescher et al. (Krausz group), Nature 419, 803 (2002)
Slide 11
Tunneling Spectroscopy
Uiberacker et al. (Krausz group), Nature 446, 627 (2007)
Slide 12
Tunneling Spectroscopy
Uiberacker et al. (Krausz group), Nature 446, 627 (2007)
Slide 13
Strong-Field Physics Experiments
Blaga et al. (Paulus, Agostini, DiMauro), Nat. Physics 5, 335 (2009)
Slide 14
Strong-Field Physics Experiments
Quan et al. Phys. Rev. Lett. 103, 093001 (2009)
Slide 15
Contents
Basics of short pulses and general concepts
Attosecond pulse generation
Mechanics of Electrons
single electrons
in strong laser fields
Attosecond Experiments with isolated Atoms
Multi-Particle Systems
Molecules
multi-electron dynamics (correlation)
Attosecond experiments with molecules / multiple electrons
Ultrafast Quantum Control
of electrons, atoms, molecules
Novel Directions/Applications
Technology
Slide 16
Contents
Multi-Particle Systems (Molecules, many electrons)
Attosecond experiments with molecules / multiple electrons
- Molecules and molecular orbitals
- Multi-electron Correlation: basics
- Born-Oppenheimer and beyond
- Recollision physics
- Experiments with Molecules
Slide 17
Chemical Bonds
http://en.wikipedia.org/wiki/Nitrogen
http://ibchem.com/IB/ibfiles/bonding/bon_img/cov2.gif,
http://www.unige.ch/sciences/Actualites/2007/MaximumMultiplicity/
W2_Mutiplicity.png
Slide 18
Linear Combination of Atomic Orbitals (LCAO)
http://www.uweb.ucsb.edu/~jodea/chem1c.htm, http://tannerm.com/images/diatomic7.gif
Slide 19
Molecular electronic structure
http://en.wikipedia.org/wiki/File:Benzene_Representations.svg
Slide 20
Complex Molecules
http://images.absoluteastronomy.com/images/encyclopediaimages/h/he/he
xokinase_ball_and_stick_model,_with_substrates_to_scale_copy.png
http://dwb4.unl.edu/Chem/CHEM869K/CHEM869KLinks/www.ccp14.ac.uk
/ccp/web-mirrors/llnlrupp/Xray/tutorial/pdb/helix_bonds.gif
Slide 21
Ultrashort x-ray/XUV Pulses
F E
ree
lectron
L
asers
and
H H
igh
armonic
wavelength
~1.5 Å
>1 nm
pulse energy
~1 mJ
<1 J
pulse duration
~100 as
~200 m ~20 fs
1 fs (proj.) fully
coherent
~1 mm
G
eneration
Slide 22
Complex Molecules
every molecule is different!
single shot!
F E
ree
L
lectron
asers
wavelength
~1.5 Å
-2 fs
2 fs
5 fs
10 fs
pulse energy
20 fs
~1 mJ
50 fs
pulse duration
~20 fs
1 fs (proj.)
Neutze et al., Nature 406, 752 (2000)
Slide 23
DNA
http://www.chemicalgraphics.com/paul/images/DNA/BallAndStick.jpg
Slide 24
macromopecular dynamics
e.g. detach functional group
(signaling protein)
from enzyme receptor
Pictures from: http://www.nfcr.org/Portals/0/Images/3d_blue_green_molecule.jpg, http://hasylab.desy.de/e77/e106/e122/e35842/e35862/Fig1_Hasylab-ultrafast_eng.jpg
Slide 25
Some theory of the chemical bond
Valence bond theory
localized electrons
between two atoms
Molecular orbital theory
delocalized electrons
within entire molecule
http://www.york.ac.uk/che
mistry/staff/academic/hn/pkaradakov/
www.jonathanpmiller.com/
become equivalent if extended
Born-Oppenheimer always inherently assumed
Slide 26
Complexity of Wavefunctions
Y ( r1 , r2 ,..., rN , s1 , s 2 ,..., s N )
Hydrogen atom (1 electron, 1 nucleus) can be found analytically
everything else: numerics necessary
for example: store wavefunctions on a grid
10 points (double precision, 8 B(Bytes)) in each dimension
Ground states (and ignoring nuclear core wavefunctions and most nuclear spin states):
Hydrogen atom: 16 kB
Helium atom:
32 MB
Hydrogen molecule:
64 GB
Oxygen atom:
21018 GB
Methane (16 daltons, [Da]): 6.51034 GB
Biomolecule: (kDa-MDa):
~101,000- 101,000,000 GB
(103(N-1) 2(N-1))8 B
- a few ZB (ZettaBytes), 1012 GB is the estimated total data stored digitally
estimate by IDC (International Data Corporation)
- 50 PB (PetaBytes), 106 GB is estimated information written by mankind in known history
Slide 27
Some theory of the chemical bond
Quantum chemistry methods
Density Functional Theory (DFT)
Hartree-Fock Theory (HF)
(single Slater determinant)
problems with ground states energetically
close to excited states or
in bond-breaking situations
improvements:
http://upload.wikimedia.org/wikipedia/en/7/7e/Electron_correlation.png
- Configuration interaction (CI)
- Multi-configurational self-consistent field (MCSCF)
combination between configuration interaction
(where the molecular orbitals are not varied but the expansion of the wave function)
and Hartree-Fock (where there is only one determinant but the molecular orbitals are varied).
- Semi-empirical quantum chemistry methods
for large molecules where other methods fail
Slide 28
Hybridization
sp2
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 29
Hybridization
sp
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 30
Hybridization
sp3
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 31
Scientific Goal of AttoPhysics
Correlated e- lectron dynamics
e-
e-
interaction (Coulomb)
(Entanglement)
Correlation
Y( e- 1, e- 2) ≠ Ψ( e- 1) ×Ψ ( e- 2)
symmetry (Fermions)
non-interacting
interacting
location e- 2
1
0
location
e- 1
Slide 32
Scientific Goal of AttoPhysics
Correlated e- lectron dynamics
e-
e-
interaction (Coulomb)
Correlation
Y( e- 1, e- 2) ≠ Ψ( e- 1) ×Ψ ( e- 2)
symmetry (Fermions)
location e- 2
interacting
non-interacting
any bonding orbital in matter
occupied
Giant Magnetoresistance typicallyHigh
Tc superconductivity
by 2 electrons
e-
efundamental role
in
radiation damage
(ionization+excitation)
Sept. 2007 location e 1
importance in
Lanzara group, UC Berkeley
life sciences
Slide 33
Two-electron dynamics
Pisharody and Jones
Science 303, 813 (2004)
– Rydberg electrons
– Barium atoms
Slide 34
Quantum Level Spacings
in a molecule
Separation: Electronic, Vibrational, Rotational
Ytotalyel,nFvib,mfrot,l
Energy
Ye,2
Ye,1
5
Ye,0
0
frot,l
Fv,n
Internuclear Distance
Slide 35
Born-Oppenheimer Approximation
Full Hamiltonian
Product Wavefunction:
Reduced Hamiltonian (internuclear only)
http://www.nat.vu.nl/~wimu/MolPhys.html
Slide 36
Estimation of Quantum Time Scales
Molecular rotation frequency
Tr=300 fs
Molecular vibration frequency
Tv=7 fs
Electron vibration frequency
Te=150 as
Electron rotation frequency
=
ħ
1
L
mpa02
2000
I
D
mp
D
me
ħ
L
=
=
2
mea0
I
1
1
2000
50
1
1
1
1
Slide 37
Recollision Physics
Paul Corkum, NRC Canada
ħ HHG
elastic scattering ATI
Strong laser field
e-e-
e-
inelastic scattering
NSDI, excitation, fragmentation
spectroscopy parameters:
- alignment angle
- laser intensity / ellipticity / wavelength / CEP, ...
- multicolor excitation
- ...
Slide 38
Three-step model
P. Corkum, Phys. Rev. Lett. 71, 1994 (1993)
Slide 39
Molecular recollision
Slide 40
linear
elliptic
atom
molecule
normalized harmonic yield
HHG ellipticity dependence
ellipticity
A. Flettner et al. (Gerber group) EPJ D (2002)
Slide 41
Argon and Nitrogen
static polarizability
Slide 42
Ellipticity experiment setup
Slide 43
Example measurement: H13 in Ar
Slide 44
Experiment and Model: Ar
Slide 45
Nitrogen vs. Argon
Slide 46
HHG-Simulation
Slide 47
Earlier Results
Slide 48
simulation results Ar vs. N2
ellipticity
Slide 49
Electron-Wavepacket -Shaping
ionization
1Å
propagation recombination
3Å
different degrees of delocalization
4Å
Slide 50
Temporal evolution in laser field
0 .4
1
0 .3
0 .2
H-Atom
0 .1
0 .0
0
1
0 .3
-1 5-2
-1 0
-5
0
5
10
215
-1 5-2
-1 0
-5
0
5
10
215
-1 5-2
-1 0
-5
0
5
10
21 5
-1 5-2
-1 0
-5
0
5
10
21 5
-1 5-2
-1 0
-5
0
5
10
21 5
0 .2
1Å
0 .1
3Å
4Å
22
|Y(y)|
|Y(p
y)|
0 .0
0
0 .2
1
0 .1
0
0 .0
0 .2
2
0 .1
1
0 .0
0
0 .2
2
y
10 Å
x
0 .1
1
0 .0
0
momentum
y coordinate
py [a.u.]
[a.u.]
Slide 51
internuclear-distance dependence
conversion efficiency (H39-H51)
3.0
2.5
2.0
1.5
1.0
atom
0.5
molecular ground state
0.0
1
2
internuclear distance [Å]
3
Inf
Slide 52
Pump–Drive Scheme
T.P. et al. Phys. Rev. A 70, 013805 (2004)
pump pulse
driver pulse
Slide 53
Molecular Tomography
Itatani et al.(Corkum, Villeneuve
Nature 432, 867 (2004)
Attosecond Flashes of Light
– Illuminating electronic quantum dynamics –
XXIIIrd Heidelberg Graduate Days
Lecture Series
Thomas Pfeifer
InterAtto Research Group
MPI – Kernphysik, Heidelberg
Slide 2
Contents Yesterday
Attosecond Pulses
Classical and quantum mechanics of electrons
- Classical Motion of Electrons
definition of important quantities
- Quantum Mechanics
· Electron dynamics in (intense) laser fields
· Ionization
- High-harmonic generation: quantum mechanical view
Slide 3
Contents
Basics of short pulses and general concepts
Attosecond pulse generation
Mechanics of Electrons
single electrons
in strong laser fields
Attosecond Experiments with isolated Atoms
Multi-Particle Systems
Molecules
multi-electron dynamics (correlation)
Attosecond experiments with molecules / multiple electrons
Ultrafast Quantum Control
of electrons, atoms, molecules
Novel Directions/Applications
Technology
Slide 4
High Harmonics Quantum Mechanical
M. Lewenstein et al. Phys. Rev. Lett. 49, 2117 (1994)
1
S ( p , t , t )
t
t
~
p eA( t )
2m
2
~
dt
Slide 5
high-harmonic generation
intense laser field acting on single atom
probability distribution p(x,y)=|Y(x,y)|2 for the electronic wavefunction
laser polarization
Slide 6
Wavepacket spreading
Slide 7
Split-Step Operator Technique
Slide 8
Streak field spectroscopy
quantum mechanically, with interference
Goulielmakis et al. (Krausz group), Science 305, 1267 (2004)
Slide 9
Streak-field spectroscopy
Drescher et al., Nature 419, 803 (2002)
Slide 10
Auger decay in Kr
Drescher et al. (Krausz group), Nature 419, 803 (2002)
Slide 11
Tunneling Spectroscopy
Uiberacker et al. (Krausz group), Nature 446, 627 (2007)
Slide 12
Tunneling Spectroscopy
Uiberacker et al. (Krausz group), Nature 446, 627 (2007)
Slide 13
Strong-Field Physics Experiments
Blaga et al. (Paulus, Agostini, DiMauro), Nat. Physics 5, 335 (2009)
Slide 14
Strong-Field Physics Experiments
Quan et al. Phys. Rev. Lett. 103, 093001 (2009)
Slide 15
Contents
Basics of short pulses and general concepts
Attosecond pulse generation
Mechanics of Electrons
single electrons
in strong laser fields
Attosecond Experiments with isolated Atoms
Multi-Particle Systems
Molecules
multi-electron dynamics (correlation)
Attosecond experiments with molecules / multiple electrons
Ultrafast Quantum Control
of electrons, atoms, molecules
Novel Directions/Applications
Technology
Slide 16
Contents
Multi-Particle Systems (Molecules, many electrons)
Attosecond experiments with molecules / multiple electrons
- Molecules and molecular orbitals
- Multi-electron Correlation: basics
- Born-Oppenheimer and beyond
- Recollision physics
- Experiments with Molecules
Slide 17
Chemical Bonds
http://en.wikipedia.org/wiki/Nitrogen
http://ibchem.com/IB/ibfiles/bonding/bon_img/cov2.gif,
http://www.unige.ch/sciences/Actualites/2007/MaximumMultiplicity/
W2_Mutiplicity.png
Slide 18
Linear Combination of Atomic Orbitals (LCAO)
http://www.uweb.ucsb.edu/~jodea/chem1c.htm, http://tannerm.com/images/diatomic7.gif
Slide 19
Molecular electronic structure
http://en.wikipedia.org/wiki/File:Benzene_Representations.svg
Slide 20
Complex Molecules
http://images.absoluteastronomy.com/images/encyclopediaimages/h/he/he
xokinase_ball_and_stick_model,_with_substrates_to_scale_copy.png
http://dwb4.unl.edu/Chem/CHEM869K/CHEM869KLinks/www.ccp14.ac.uk
/ccp/web-mirrors/llnlrupp/Xray/tutorial/pdb/helix_bonds.gif
Slide 21
Ultrashort x-ray/XUV Pulses
F E
ree
lectron
L
asers
and
H H
igh
armonic
wavelength
~1.5 Å
>1 nm
pulse energy
~1 mJ
<1 J
pulse duration
~100 as
~200 m ~20 fs
1 fs (proj.) fully
coherent
~1 mm
G
eneration
Slide 22
Complex Molecules
every molecule is different!
single shot!
F E
ree
L
lectron
asers
wavelength
~1.5 Å
-2 fs
2 fs
5 fs
10 fs
pulse energy
20 fs
~1 mJ
50 fs
pulse duration
~20 fs
1 fs (proj.)
Neutze et al., Nature 406, 752 (2000)
Slide 23
DNA
http://www.chemicalgraphics.com/paul/images/DNA/BallAndStick.jpg
Slide 24
macromopecular dynamics
e.g. detach functional group
(signaling protein)
from enzyme receptor
Pictures from: http://www.nfcr.org/Portals/0/Images/3d_blue_green_molecule.jpg, http://hasylab.desy.de/e77/e106/e122/e35842/e35862/Fig1_Hasylab-ultrafast_eng.jpg
Slide 25
Some theory of the chemical bond
Valence bond theory
localized electrons
between two atoms
Molecular orbital theory
delocalized electrons
within entire molecule
http://www.york.ac.uk/che
mistry/staff/academic/hn/pkaradakov/
www.jonathanpmiller.com/
become equivalent if extended
Born-Oppenheimer always inherently assumed
Slide 26
Complexity of Wavefunctions
Y ( r1 , r2 ,..., rN , s1 , s 2 ,..., s N )
Hydrogen atom (1 electron, 1 nucleus) can be found analytically
everything else: numerics necessary
for example: store wavefunctions on a grid
10 points (double precision, 8 B(Bytes)) in each dimension
Ground states (and ignoring nuclear core wavefunctions and most nuclear spin states):
Hydrogen atom: 16 kB
Helium atom:
32 MB
Hydrogen molecule:
64 GB
Oxygen atom:
21018 GB
Methane (16 daltons, [Da]): 6.51034 GB
Biomolecule: (kDa-MDa):
~101,000- 101,000,000 GB
(103(N-1) 2(N-1))8 B
- a few ZB (ZettaBytes), 1012 GB is the estimated total data stored digitally
estimate by IDC (International Data Corporation)
- 50 PB (PetaBytes), 106 GB is estimated information written by mankind in known history
Slide 27
Some theory of the chemical bond
Quantum chemistry methods
Density Functional Theory (DFT)
Hartree-Fock Theory (HF)
(single Slater determinant)
problems with ground states energetically
close to excited states or
in bond-breaking situations
improvements:
http://upload.wikimedia.org/wikipedia/en/7/7e/Electron_correlation.png
- Configuration interaction (CI)
- Multi-configurational self-consistent field (MCSCF)
combination between configuration interaction
(where the molecular orbitals are not varied but the expansion of the wave function)
and Hartree-Fock (where there is only one determinant but the molecular orbitals are varied).
- Semi-empirical quantum chemistry methods
for large molecules where other methods fail
Slide 28
Hybridization
sp2
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 29
Hybridization
sp
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 30
Hybridization
sp3
http://www.grandinetti.org/Teaching/Chem121/Lectures/Hybridization/
Slide 31
Scientific Goal of AttoPhysics
Correlated e- lectron dynamics
e-
e-
interaction (Coulomb)
(Entanglement)
Correlation
Y( e- 1, e- 2) ≠ Ψ( e- 1) ×Ψ ( e- 2)
symmetry (Fermions)
non-interacting
interacting
location e- 2
1
0
location
e- 1
Slide 32
Scientific Goal of AttoPhysics
Correlated e- lectron dynamics
e-
e-
interaction (Coulomb)
Correlation
Y( e- 1, e- 2) ≠ Ψ( e- 1) ×Ψ ( e- 2)
symmetry (Fermions)
location e- 2
interacting
non-interacting
any bonding orbital in matter
occupied
Giant Magnetoresistance typicallyHigh
Tc superconductivity
by 2 electrons
e-
efundamental role
in
radiation damage
(ionization+excitation)
Sept. 2007 location e 1
importance in
Lanzara group, UC Berkeley
life sciences
Slide 33
Two-electron dynamics
Pisharody and Jones
Science 303, 813 (2004)
– Rydberg electrons
– Barium atoms
Slide 34
Quantum Level Spacings
in a molecule
Separation: Electronic, Vibrational, Rotational
Ytotalyel,nFvib,mfrot,l
Energy
Ye,2
Ye,1
5
Ye,0
0
frot,l
Fv,n
Internuclear Distance
Slide 35
Born-Oppenheimer Approximation
Full Hamiltonian
Product Wavefunction:
Reduced Hamiltonian (internuclear only)
http://www.nat.vu.nl/~wimu/MolPhys.html
Slide 36
Estimation of Quantum Time Scales
Molecular rotation frequency
Tr=300 fs
Molecular vibration frequency
Tv=7 fs
Electron vibration frequency
Te=150 as
Electron rotation frequency
=
ħ
1
L
mpa02
2000
I
D
mp
D
me
ħ
L
=
=
2
mea0
I
1
1
2000
50
1
1
1
1
Slide 37
Recollision Physics
Paul Corkum, NRC Canada
ħ HHG
elastic scattering ATI
Strong laser field
e-e-
e-
inelastic scattering
NSDI, excitation, fragmentation
spectroscopy parameters:
- alignment angle
- laser intensity / ellipticity / wavelength / CEP, ...
- multicolor excitation
- ...
Slide 38
Three-step model
P. Corkum, Phys. Rev. Lett. 71, 1994 (1993)
Slide 39
Molecular recollision
Slide 40
linear
elliptic
atom
molecule
normalized harmonic yield
HHG ellipticity dependence
ellipticity
A. Flettner et al. (Gerber group) EPJ D (2002)
Slide 41
Argon and Nitrogen
static polarizability
Slide 42
Ellipticity experiment setup
Slide 43
Example measurement: H13 in Ar
Slide 44
Experiment and Model: Ar
Slide 45
Nitrogen vs. Argon
Slide 46
HHG-Simulation
Slide 47
Earlier Results
Slide 48
simulation results Ar vs. N2
ellipticity
Slide 49
Electron-Wavepacket -Shaping
ionization
1Å
propagation recombination
3Å
different degrees of delocalization
4Å
Slide 50
Temporal evolution in laser field
0 .4
1
0 .3
0 .2
H-Atom
0 .1
0 .0
0
1
0 .3
-1 5-2
-1 0
-5
0
5
10
215
-1 5-2
-1 0
-5
0
5
10
215
-1 5-2
-1 0
-5
0
5
10
21 5
-1 5-2
-1 0
-5
0
5
10
21 5
-1 5-2
-1 0
-5
0
5
10
21 5
0 .2
1Å
0 .1
3Å
4Å
22
|Y(y)|
|Y(p
y)|
0 .0
0
0 .2
1
0 .1
0
0 .0
0 .2
2
0 .1
1
0 .0
0
0 .2
2
y
10 Å
x
0 .1
1
0 .0
0
momentum
y coordinate
py [a.u.]
[a.u.]
Slide 51
internuclear-distance dependence
conversion efficiency (H39-H51)
3.0
2.5
2.0
1.5
1.0
atom
0.5
molecular ground state
0.0
1
2
internuclear distance [Å]
3
Inf
Slide 52
Pump–Drive Scheme
T.P. et al. Phys. Rev. A 70, 013805 (2004)
pump pulse
driver pulse
Slide 53
Molecular Tomography
Itatani et al.(Corkum, Villeneuve
Nature 432, 867 (2004)