Dynamique Quantique des Systemes ComplexesVers les Nanostructures et les Environnements Biologiques
Irene Burghardt
Pole Theorie, Departement de Chimie, UMR 8640, Ecole Normale Superieure, Paris
Journee Annuelle de la Chimie 2009-2010UFR de Chimie UPMC
Concepts/Models/SystemsMethods
Perspectives
Agenda
1 Concepts/Models/Systems: From Polyatomics to Extended SystemsExciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
2 Methods: Quantum & Quantum-Classical Dynamics in Many DimensionsMulticonfigurational MethodsEffective-Mode ModelsQuantum-Classical Phase-Space & Density Functional Methods
3 Perspectives - Towards Quantum and Classical TransportExciton DynamicsProcesses at InterfacesClassical Transport Phenomena
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Agenda
1 Concepts/Models/Systems: From Polyatomics to Extended SystemsExciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
2 Methods: Quantum & Quantum-Classical Dynamics in Many DimensionsMulticonfigurational MethodsEffective-Mode ModelsQuantum-Classical Phase-Space & Density Functional Methods
3 Perspectives - Towards Quantum and Classical TransportExciton DynamicsProcesses at InterfacesClassical Transport Phenomena
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Agenda
1 Concepts/Models/Systems: From Polyatomics to Extended SystemsExciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
2 Methods: Quantum & Quantum-Classical Dynamics in Many DimensionsMulticonfigurational MethodsEffective-Mode ModelsQuantum-Classical Phase-Space & Density Functional Methods
3 Perspectives - Towards Quantum and Classical TransportExciton DynamicsProcesses at InterfacesClassical Transport Phenomena
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Goals in a Nutshell
Charge TransferEnergy & Non−Equilibrium
Transport& Nuclear DynamicsElectronic Structure
Microscopic
Extended, Nano−Structured
Biological & Material Systems
e.g. for PhotovoltaicsCoherent Control
Photo−Excitation, Dissipation,
Decoherence
& Optimization
Understanding
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Can We Put to Use Our Knowledge of Reactivity &Photochemistry?
A. Piryatinski, http://cnls.lanl.gov/External/people/AndreiPiryatinski.php
Many processes require (non-adiabatic) quantum dynamics
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Landmark Topology: Conical Intersections (CoIn’s)
CoIn = photochemical funnel
Schultz et al., J. Am. Chem. Soc. 125, 8098 (2003)
• CoIn topology highly anharmonic
• Extreme breakdown of theBorn-Oppenheimer approximation
• Ultrafast decay (fs to ps scale)
• CoIn’s are ubiquitous(Truhlar/Mead:“Principle ofnon-rareness of CoIn’s”)
• Polyatomic molecules; Jahn-Tellereffect in solids
Koppel, Domcke, Cederbaum, Adv. Chem. Phys. 57, 59 (1984)
Conical Intersections, Eds. Yarkony, Koppel, Domcke (2004)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Photochemistry of “Complex” Systems
• polyatomic molecules
• solute-solvent systems
• biological chromophores & photoswitches
• extended systems, e.g., semiconducting polymers
• molecular nano-scale assemblies
• ultrafast processes (fs–ps)
• quantum coherence & decoherence
• special topologies, e.g., CoIn’s
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Methods for “Large” Systems
Approximate Potentials
& Approximate Dynamics
On−The−Fly Electronic Structure
& Classical / Semiclassical Dynamics
Parametrized Model Hamiltonians
& Accurate Quantum Dynamics
Accurate Potentials
& Accurate Quantum Dynamics
Vibronic Coupling & Lattice Models;
Accurate Multiconfigurational
Techniques (MCTDH)
High−Level or Semi−Empirical
Electronic Structure Methods;
Surface Hopping,
Gaussian Wavepackets
Dyn
am
ics A
ccu
racy
Electronic Structure Accuracy
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Example 1: How Do Excitons Dissociate at aPolymer Interface (Heterojunction)?
exciton = electron + hole
photovoltaic devices, organic light-emitting diodes (OLED’s), . . .
Peumans, Uchida, Forrest, Nature 125, 8098 (2003)
F8BT:
TFB:
NNS
NN
RR
R
R
RR
N
SN
R
R
molecular-level understanding of interactions & dynamicsat the polymer interface is required
collaboration with Eric R. Bittner (Univ. Houston)Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Zeroth-Order Picture of a Heterojunction
Kar
ab
un
arliev
&B
ittn
er,
J.C
hem
.P
hys
.1
18
,4
29
1(2
00
3)
polymer/polymer interface:
F8BT
1.92eV
-3.54eV
3.16 eV
PFB/TFB
-2.75 eV (PFB)
-2.98eV (TFB)
• HOMO/LUMO valence/conduction band• 1st bound excited state: singlet exciton (1B−u in PPV); Frenkel type exciton• @junction: compare band offset vs. exciton binding energy (εB ∼ 0.5 eV)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Objective: Molecular-Level Perspective of Exciton Dissociation
TFB:F8BTheterojunction
exciton
-2.98 eV
1.92 eV
h
Ground state
Exciton state
Charge transfer
state
hole
+-
(A)
(C) F8BT (e-acceptor)
Lattice
distortion
h
0
(B)
e-donore-acceptor
-3.54 eV
3.16 eV
TFB (e-donor)
Ta
mu
ra,
Bit
tner
,B
urg
har
dt,
JCP
12
6,
02
11
03
(20
07
)
• initial photogeneration of an exciton state (XT, bright state)
• exciton decay to an interfacial charge transfer state (CT, exciplex)
• the XT CT transition is mediated by electron-phonon coupling
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
3-State Electron-Phonon Coupling Model
2.0
2.2
2.4
2.6
2.8
3.0
displacement
Energy@eVD
XT
IS
CT
parameterization for TFB:F8BT:polymer lattice model based on dimer;TDDFT and semi-empirical (PM3) calculations+ Wannier-function representation
Bittner et al., JCP 122, 214719 (2005)
H =N∼30
∑i
Hi = ∑i
ωi
2
(p2
i + x2i
)+V lin
i
V lini =
κ(1)i xi λ
(12)i xi λ
(13)i xi
λ(12)i xi κ
(2)i xi λ
(23)i xi
λ(13)i xi λ
(23)i xi κ
(3)i xi
state 1 = exciton (XT) statestate 2 = charge transfer (CT) statestate 3 = intermediate (IS) state
phonons = C=C stretch + ring torsions
Tamura, Ramon, Bittner, Burghardt, J. Phys. Chem. B 112, 10269 (2008)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Quantum Dynamics of Exciton Dissociation
3-state
2-state
• 3-state 28-mode model
• MCTDH calculations
• sample over relevantinterface configurations
• intermediate statesplay a key role
• qualitative agreementwith time-resolvedphotoluminescence
Tamura, Ramon, Bittner, Burghardt,
Phys. Rev. Lett. 100, 107402 (2008)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Interface Configurations: Role of Stacking
eclipsed: π-stacked F8 units
staggered: F8 units displaced
Note: F8’s electro-positive in F8BT but electro-negative in TFB
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Example 2: Excitation Energy Transfer (EET)
photosynthesis, (artificial) light-harvesting systems
Tamura, Burghardt, in preparation
H = ∑i
ωi
2
(p2
i + x2i
)+
(κ
(1)i x(1)
i VCoulomb12
VCoulomb12 κ
(2)i x(2)
i
)
VCoulomb12 =
∫drD drA
ρ(eg)D (rD)ρ
(ge)A (rA)
|rD− rA|• inter-monomer couplings via transition densities• generalization of Forster rate theory & transition dipole approximation
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Ultrafast, Coherent Regime:Excitation Transfer Coupled to Porphyrin Effective Mode(s)
Tamura, Burghardt, in preparation 0
0.2
0.4
0.6
0.8
1
0 500 1000 1500
site
pop
ulat
ion
time [fs]
site 1: initial excitation
23 4 5 6 7 8 9
• significantly different from non-coherent, Forster (FRET) type transfer
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
EET in Functionalized Assemblies
e.g., carbon nanotubes (CNT) or quantum dots (QD) as donor/acceptor species
ANR project “Experimental and theoretical study of energy andcharge transfer in nanotube/chromophore compounds”, submitted
Tamura, Mallet, Oheim, Burghardt, J. Phys. Chem. C, 113, 7548 (2009)
• FRET1 labeling in biological/medical applications; photovoltaics
• again, pronounced non-Forster effects, esp. for elongated nano-objects
1FRET = Fluorescence Resonance Energy TransferIrene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Example 3: Biological Switches, e.g., PYPPYP = Photoactive Yellow Protein
isomerisation constrained by “protein nanospace”
Tyr98
P h e 96
A rg 5 2
C h ro m o p h o re
C ys 6 9
P h e 6 2V a l6 6
Th r5 0
G lu 4 6
Tyr4 2
(a)
O
S
O
CNRS/DFG collaboration ENS/Heidelberg; Gromov, Burghardt, Koppel, Cederbaum, JACS 129, 6798 (2007)
• excited-state lifetime ∼ 700 fs (in solution ∼ 10 ps)
• the local amino acid environment is of key importance
• how is the chromophore’s quantum dynamics concerted with theenvironmental dynamics/fluctuations?
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
A Complicated Photo-Switch . . . Two Isomerisation Pathways
O O
H
H
O
H
H
O
S CH3
a
b
Phenol part
Alkene part
• two S1 minima; β min. near a CoIn
• charge distributions inverted atthese two minima
0.0
1.0
2.0
3.0
En
erg
y(e
V)
-0.53/-0.47-0.25/-0.75 -0.76/-0.24
-0.39/-0.61
-0.87/-0.13
-0.71/-0.29
S 0,eqS 1,mina
S 1,minb
S1
S1
S0
S0
S1
S0
Gromov, Burghardt, Koppel, Cederbaum, JACS 129, 6798 (2007)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
The Amino Acid Environment “Tunes” the Chromophore
CC2supermolecularcalculations
Impact of Impact of the active site amino acidsthe active site amino acids
E.V. Gromov, I. Burghardt, H. Köppel, L.S. Cederbaum, JACS 129 (2007) 6798
2.8
3.2
3.6
4.0
4.4
4.8
En
erg
y(e
V)
IP
IP� -� 2
*
� -� 1*
n - � 1*
� -� 1*
nPh-
� 1*
� - � 2*
�-Arg52 � -� 1*
nPh-
� 1*
nPh-
� 1*
� -� 1*
�-Arg52
nPh-
� 1*
� - � 1*
� - � 1*
� - � 1*
�-Arg52
� - � 2* � - � 2
*
n - � 1*
� - � 1*
n - � 1*
nPh-
� 1*
�-Arg52
� - � 1*
n -� 1*
nPh-
� 1*
� -� 2*
Arg
52
Phe96
Tyr98
Glu46 Tyr42
SC
H3
O
HO
Arg
52
Arg
52
Phe6
2
Arg
52
Thr50
Va
l66
Arg
52
Arg
52
Va
l66
Tyr98
Thr50
Glu46 Tyr42
Arg
52
Va
l66
Tyr98
Thr50
Glu46 Tyr42
pCTM pCTM I II III IV V VI VII�
n -� 1*
SC
H3
O
O
SC
H3
O
O
Cy
s69
SOO
SC
H3
O
O
SC
H3
O
O
SC
H3
O
O
SC
H3
O
O
Cy
s69
SO
O
Gromov, Burghardt, Koppel, Cederbaum, J. Am. Chem. Soc. 129, 6798 (2007)
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Hierarchical Treatment of Complex, Structured Systems
Hybrid methods for quantum dynamics & electronic structure
Primary zone:
• dominant modes in many-atomsystems
• chromophore (in solution,protein)
Secondary zone:
• intramolecular “bath”
• first solvent shell (microscopicor mesoscopic description)
modes
}{ϕ(κ)
primary
modes
}{χ(n)
dissipative
secondary
modes
{g(f)}
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Just Appeared
› springer.com
isbn 978-3-642-02305-7
123
Energy Transfer Dynamics in Biom
aterial Systems
! is book presents a collection of 14 review articles that cover the key topics addressed in the workshop Energy Flow Dynamics in Biomaterial Systems which was held in October 2007 in Paris. ! ese reviews illustrate the many facets of today’s theoretical picture of electronic and vibronic dynamics and transport phenomena in biological, biomimetic, and molecular electronic systems. Part I focuses on excitation energy transfer in photosynthetic re-action centers and other multichromophoric systems, part II gives a tour d’horizon of DNA research, and part III addresses molecular electronics and quantum transport in organic materials. Finally, parts IV and V cover recent methodological developments in open system dynamics and hybrid quantum-classical methods. ! e scope of the book is deliberately broad in terms of physical systems studied and yet uni( ed in the use of quantum dynamical methods to describe transient and o) en ultrafast energy and charge transfer events in complex systems.
Burghardt · May · M
icha Bittner Ed
s.
Springer Series in Chemical Physics 93
Irene BurghardtVolkhard MayDavid A. MichaEric R. BittnerEditors
Energy Transfer Dynamics in Biomaterial Systems
1
SPRINGER SERIES IN CHEMICAL PHYSICS 93
Energy Transfer Dynamics in Biomaterial Systems
Irene BurghardtVolkhard MayDavid A. MichaEric R. BittnerEditors
Irene Burghardt Dynamique Quantique des Systemes Complexes
Concepts/Models/SystemsMethods
Perspectives
Exciton Dissociation at Organic Semiconductor JunctionsExcitation Energy Transfer (EET)Photobiological Systems
Acknowledgments & Collaborations
• E. R. Bittner (University of Houston)
• L. Cederbaum, H. Koppel, E. Gromov, E. Gindensperger(University of Heidelberg)
• G. A. Worth (University of Birmingham, UK)
• K. H. Hughes (University of Bangor, UK)
• H. Tamura (ENS Paris, now Tohoku University)
• S. Zhao, P. Ramanathan, F. Martelli (Group ENS)
Thanks to: CNRS, ANR (France) for financial support
Irene Burghardt Dynamique Quantique des Systemes Complexes