LBNL Oct.

1, 2010
Oleg Prezhdo
U. Rochester
Photoinduced Electron Transfer
at Molecule-Semiconductor Interfaces:
A Time-Domain Ab Initio Perspective
Adiabatic vs. Nonadiabatic MD
electrons treated quantum-mechanically
nuclei treated classically
e e
e
e
e
e
Nonadiabatic MD: Coupling
between potential surfaces
opens channels for system to
change electronic states.
transition allowed
weak coupling
strong coupling
Time-Domain DFT for
Nonadiabatic Molecular Dynamics
( )

=
p
p
x x
2
) ( ( ) ( ) ( )
SD
N v q p
t x t x t x , , ,
2 1
= +
Electron density derives from Kohn-Sham orbitals
H ( ) t R
DFT functional depends on nuclear evolution
( )
( ) t x H
t
t x
i
p
p
,
,

=
c
c
2 , 1 = p
Variational principle gives
|
|
.
|

\
|
V =
-

-

R i c c i
R
| o
o|
|
|
| o
_ _ o c
Orbitals are expanded in adiabatic KS basis
( ) ( ) ( )

=
o
o o
_ x t c t x
p p
,
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) t R x t R t R x t R x H ; ; ;
o o o
_ c _ =
How to think of bulk-molecule interface:
Cluster models or MOs weakly coupled to bands?
Electron-vibrational relaxation (heating):
Which phonons are involved and why?
General Questions
Dye-Sensitized Semiconductor
Solar Cell
Oregan, Gratzel Nature 353 6346 (1991)
Photovoltaics:
optimize voltage, current,
photo yield
electron transfer mechanism
and its properties
Molecule-bulk interface:
little understood in
molecular-electronics
and other fields
The electron transfer did not involve redistribution of vibrational excitation energy and was
completely different from the well known Marcus-Levich-Jortner-Gersicher mechanism.
Burfeindt, Hannappel, Storck, Willig JPC 101 6799 (1997)
A new mechanism, not Marcus-Levich-Jortner-Gerischer ?
Reaction Mechanism ?
One possibility for the observed fast injection is a strong coupling of the dcbpy t* orbital with
TiO
2
, leading to an adiabatic electron transfer from dcbpy to TiO
2
.
However, it is unclear whether strong coupling is necessary a large accepting state density
in TiO
2
would also give rise to an ultrafast injection time even when the coupling is weak.
Asbury, Ellingson, Ghosh, Ferrere, Nozik, Lian JPC 103 3110 (1999)
Adiabatic or Non-adiabatic ?
dye
dye
TiO
2
TiO
2
Types of Photoexcitation

TiO
2
-Alizarin TiO
2
-Catechol, Ru-dyes
VB
VB
CB CB
dye*
dye*
dye
dye
Electronic State Densities
Alizarin Motion
Vibrationally Induced Dynamics
of Electronic Energy Levels
Dynamics of Electronic
Energy and Coupling
E
n
e
r
g
y
L
o
c
a
l
i
z
a
t
i
o
n
(
d
y
e
/
s
e
m
i
c
o
n
d
.

c
o
u
p
l
i
n
g
)
surface OH
Photoexcited state oscillates around the CB edge
Surface OH contribute to state localization, but not energy
Photoexcited
State Energy and Localization
Distribution of Excite State Energies
~40 vibrations give Gaussian distribution of excited state energy
alizarin excited state delocalizes into CB at high energy
Localization of Photoexcited
State on Alizarin
Alizarin ET, simulation
Duncan, Stier, Prezhdo Adv. Mater. 16 240 (2004)
JACS 127 7941 (2005)
total
adiab.
NA
Experiment 6 fs, theory 8 fs
Adiabatic ET dominates over non-adiabatic ET
Photoexcited state is 30% delocalized onto TiO
2
Inside
conduction band
initial state dynamics final state
Multiple entrances
into conduction band
initial state dynamics final state
Single entrance
into conduction band
initial state dynamics final state
Adiabatic ET vs. Temperature
14 1
2.8 10 x s v

=
13 1
2 10
dye
x s v

=
K G 50 ~ A
( ) kT G k
ET
/ exp A =v
low barrier, hard to see T-dependence experimentally
multiple acceptor states speed up transfer
Electron Relaxation Inside TiO
2
relaxation time is nearly independent of initial energy
Role of Electrolyte
Fisher, Peter, Ponomarev, Walker, Wijayantha, J. Phys. Chem. B. 2000, 104, 949.
One of the main reasons for efficiency loss
I
2
dissociates off TiO
2
I
2
-
binds to TiO
2
Electron-Hole
Recombination
1.5-2.6 ps
in experiment
(very fast!)
Complete Sequence of Events
(based on alizarin simulation)
VOLTAGE
Injection at CB edge
CURRENT
Anneal surface traps
Keep electrolyte away from surface
METAL-LIGAND vs. ORGANIC DYE
Excited state towards surface
Ground state away from surface
Slower vibrational modes
Practical Considerations
a short-lived ( 15 fs) state
2.4 eV above the Fermi level
Defect States
O
2-
VB
Ti
4+
CB
E
F
E
vac
e
-
TiO
2
H
2
O
Wet-Electrons on TiO
2
Petek: Science 308 1154 (2005); 311 1436 (2006)
Charge density of wet-electron state supported via
dangling H atoms on the surface
H
2
O more important than OH
High level of charge delocalization over TiO
2
substrate
Fischer, Duncan, Prezhdo J. Am. Chem. Soc. 131 15483 (2009)
Wet-e: Electronic States
Thermal fluctuations distort geometry, affecting electronic dynamics
Changes in the Ti-O bond lengths/angles affect the electrostatic interactions
between the H
2
O and the substrate surface
Wet-e: Surface Motions
Fischer, Duncan, Prezhdo J. Am. Chem. Soc. 131 15483 (2009)
Surface layers shift sideways
Energy is affected by movement of surface hydrogen atoms,
while localization depends mostly on motion of heavier atoms
Energy
Localization
(donoracceptor
coupling)
Active Phonon Modes
Fischer, Duncan, Prezhdo J. Am. Chem. Soc. 131 15483 (2009)
Strong coupling & high TiO
2
DOS favor ultrafast ET
ET starts from a state with significant TiO
2
contribution
NA & adiabatic ET mechanisms play equal roles
Electron Transfer Dynamics
Displays similar characteristics to dye-semiconductor systems
Ultrafast ET driven by relatively low frequency vibrational modes
Both adiabatic and NA mechanisms are important
Wet-electron differs in being a true interfacial state
Results have practical implications
TiO
2
is a popular electrode material and the wet-electron state is likely to
play role in electro-chemical photolysis, e.g. water splitting
Provides fundamental understanding for the role of electrolyte in dye-
sensitized semiconductor solar cells
Wet-e: Conclusions
How to think of bulk-molecule interface:
Cluster models or MOs weakly coupled to bands?
Electron-vibrational relaxation (heating):
Which phonons are involved and why?
General Questions
-

V R i
R
| o
_ _
TiO
2
particle size effect on ET dynamics
Polymer on TiO
2
Reverse process: CdSe to a dye
Quantum dot on TiO
2
Realistic models of electrolyte
Role of triplet, etc. states in Ru-dyes
Chromophore diads
Anatase-Rutile interface
Current & Future Projects
Annu. Rev. Phys.Chem. 58 143 (2007)
Acc. Chem. Res. 41 339 (2008)
Prog. Surf. Sci. 84 39 (2009)
J. Phys. Chem. B 106 8047 (2002)
J. Mol. Struct 630 33-43 (2003)
Isr. J. Chem. 42 213-224 (2003)
Adv. Mater. 16 240 (2004)
J. Am. Chem. Soc. 127 7941 (2005)
J. Phys. Chem. B 109 365 (2005)
J. Phys. Chem. B 109 17998 (2005)
Phys. Rev. Lett. 95 163001 (2005)
J. Am. Chem. Soc. 129 8528 (2007)
J. Am. Chem. Soc. 130 9756 (2008)
J. Am. Chem. Soc. 131 15483 (2009)
Book Chapters: Elsevier (2006), Springer (2007)
Publications
Bill Stier (UT-Austin)
Walter Duncan (Schrodinger Inc.)
Zhenyu Guo (visitor from China)
Sean Fischer (current student)
DOE, NSF
Acknowledgments