Terthiophene Dihedral Scan

20 40 60 80 100 120 140 160 180

E

(
e
V
)
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
B
o
l
t
z
m
a
n
n

P
o
p
u
l
a
t
i
o
n
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
Tetramer(Gas)
Tetramer(CHCl3)
Hexamer(Gas)
Boltzmann Population for Tetramer (Gas)
Initial Structures for Molecular Morphologies

}
A
A
=
) / exp(
) / exp(
kT E d
kT E
P
|
|
|
|
For thermodynamic equilibrium
Examples of Polymer Conformations
Transition Densities
(nm)
300 350 400 450 500 550
C
a
l
c
u
l
a
t
e
d

A
b
s
o
r
b
a
n
c
e
0.0
0.2
0.4
0.6
0.8
1.0
1.2
TD-DFT
B3LYP/6-31G*
100 Polymer Conformations
Excitation Energies (S
1
to S
4

) broadened by 0.1 eV
20 40 60 80 100 120 140 160 180
E

(
e
V
)
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
B
o
l
t
z
m
a
n
n

P
o
p
u
l
a
t
i
o
n
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
Tetramer(Gas)
Tetramer(CHCl3)
Hexamer(Gas)
Boltzmann Population for Tetramer (Gas)
}
A
A
=
) / exp(
) / exp(
kT E d
kT E
P
|
|
|
|
Monomer Transition Density Population Analysis
Calculated TD Size (# units)
3 4 5 6 7 8 9
#

o
f

P
o
l
y
m
e
r
s
0
5
10
15
20
25
Calcualted Transition (S
0
-S
n
)
0 1 2 3 4 5
A
v
e
r
a
g
e

T
D

S
i
z
e

(
#

m
o
n
o
m
e
r
s
)
5.7
5.8
5.9
6.0
6.1
6.2
Transition Densities Calculated in DFT are a LCAO. Approach to quantify TD size:
(
(
(
(

= =

N
n m
m n
m
m n
c
c
c
c
c

2
1
,
,
n
n is the monomer number
m is over all atoms in a monomer
Count in from either end of a
polymer until a monomer
contains a certain percentage of
the TD (in this case 5 %)
High MW vs. Low MW P3HT
Wavelength (nm)
300 400 500 600 700
N
o
r
m
a
l
i
z
e
d

A
b
s
o
r
b
a
n
c
e
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
N
o
r
m
a
l
i
z
e
d

P
L
0.0
0.2
0.4
0.6
0.8
1.0
1.2
High MW
Low MW
The low MW P3HT has a higher regioregularity