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Letter
Atomistic Simulations of Charge Separation at a Nano-Hybrid Interface: Relevance of Photoinduced Initial State Preparation Thomas Plehn, Dirk Ziemann, and Volkhard May J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b02772 • Publication Date (Web): 21 Dec 2017 Downloaded from http://pubs.acs.org on December 21, 2017
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The Journal of Physical Chemistry Letters is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
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⇤
ħω e-
x10-5
Popula on
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The Journal of Physical Chemistry Letters
Xtot
CStot
Time [fs]
h+
ZnO
X p-6P
⇡
⇤
ACS Paragon Plus Environment
The Journal of Physical Chemistry Letters
a)
20
b)
m=3 m=2 m=1
para-sexiphenyl
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H(t) =
X m
+
Em |
X m,n
+ c)
X
X m
2 m=1
m ih
Vmn |
a
+
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m| m ih
Va |
+
X m,a
n|
1a ih
Vm (t)|
+
X
a,m,n 1|
m ih
Ema |
ma ih
Vmn |
ma | ma ih
na |
+
|+
.
ZnOH 3783 atoms
⇡
X Em
|Xm i
Eeg 0
1
Eeg = 4.02
X Em
|CSma i
E+g
EG CS Ema
Ea
a
|Xm i
|Gi
X Em
m |CSma i m
CS Ema
Vmn
a
Vmn
ACS Paragon Plus Environment
a)
c)
Population
x10-2 ℏωL=4.35 eV
x10-5
x10-5 ℏωL=4.0 eV
x10-5 Time [fs]
Time [fs] d)
HT Vmm±1 = V HT
V
HT
x10-3 ℏωL=4.2 eV
x10-3
Population
b) Population
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The Journal of Physical Chemistry Letters
Population
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x10-6
ℏωL=3.9 eV
x10-6 Time [fs]
Time [fs]
P P a
VaCT
~!L
V P
= 0.2
~!L V = 0.02
P
A
x
A x
A
A
a A
=
P
a ca
ca
a
i~@/@t| (t)i = He↵ (t)| (t)i ˆ He↵ (t) = H(t) + Fˆ (t) + D(t) H(t)
VaCT = ca V CT
V CT V CT
A
Fˆ (t)
ˆ D(t) Fˆ
Vm (t)
~!L
⌧p = 100
ACS Paragon Plus Environment
ˆ D
The Journal of Physical Chemistry Letters
PX (t) =
X m
PCS (t) =
X m,a
6
|hXm | (t)i|2
5
|hCSma | (t)i| ,
4
D
~!L = 4.2
C
PCS
X
2
B
1
V CT
3
=
X m
cX m (↵)|Xm i +
X m,a
A
A
100/0 50/50 0/100
cCS ma (↵)|CSma i
V
CS Absorption [a.u.]
= 0.2
V
= 0.02
V
= 0
~!L
>
V CT = 0
ACS Paragon Plus Environment
B
1
State Character [%/%]
↵i
C
2
III
|
D
3
P
~!L = 3.9 P
~!L ~!L = 4.35
II
I
6
2
~!L V CT = 0.2
V HT = 0.02
5
4
Energy [eV]
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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mol. index m Time [ps]
ħωL=4.2 eV
b)
ħωL=4.0 eV
c)
d)
ħωL=3.9 eV
X molecular index m
a)
ħωL=4.35 eV
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The Journal of Physical Chemistry Letters
~!L = 4.35 ħωL
~!L = 4.2
Time [ps] P (m, t) V ~!L
V
= 0.2
= 0.02
m
~!L = 4.0
~!L = 3.9 ~!L
P
~!L = 4.35
PCS (t) | P
~!L
↵i
↵ c↵ (t)| ↵ i
P
P
~!L = 4.0 PH (m, t)
PCS
~!L = 3.9
m
~!L = 4.2
PX (m, t)
PH (m, t)
V
= 0.02
m m PX (m, t)
~!L = 4.35
ACS Paragon Plus Environment
V
The Journal of Physical Chemistry Letters
mol. index m Time [ps]
ħωL=4.2 eV
b)
ħωL=4.0 eV
c)
d)
H+
molecular index m
a)
ħωL=4.35 eV
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m
