ZnO p-6P

h+ ħω. Time [fs]. P op ula on x10-5. Xtot. CStot. ZnO p-6P. *. ⇡. Page 1 of 8. ACS Paragon Plus Environment. The Journal of Physical Chemistry Let...
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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

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

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

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

H(t) =

X m

+

Em |

X m,n

+ c)

X

X m

2 m=1

m ih

Vmn |

a

+

Page 2 of 8

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

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

The Journal of Physical Chemistry Letters

Population

Page 3 of 8

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

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

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

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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m