3.

Chain conformation
3.1 Constitution, configuration, conformation
Macromolecule build-up from large number of small, connected subunits
(monomers)
a) Constitution: The constitution of a macromolecule describes the type and
the order of the subunits (monomers) and the resulting molecular structure.
Example:

... AAAAAAAAAAA ...

homopolymer

... ABABABABABA ...

alternating copolymer

... AAAABBBBBBB ...

diblock copolymer

... AAAABBBBBBB ...

|
|
B
A
|
|
B
A
|
|
B
A
graft-copolymer
Other examples:

statistical copolymer, star-polymer, ...

b) Configuration: describes the spatial position of atoms within the molecule:

The geometrical arrangement in polymers arising from the order of atoms
determined by chemical bonds.
The regularity and symmetry of the side-groups can affect strongly the
properties of polymers. Side groups are atoms or molecules with free
bonds, called free-radicals, like H, O, methyl, etc.
The configuration of a polymer cannot be altered unless chemical bonds
are broken and reformed.
asymmetric C-atom
all substituents are different
Chapter 03

Example: Alanin

Tacticity: The orderliness of the succession of configurationally repeating units

in the main chain of a polymer molecule (important for crystallization).
if the radicals are linked in the same order, the configuration is called
isotatic
in a stereoisomer in a syndiotactic configuration, the radical groups are at
alternative sides in the chain
in the atactic configuration, the radical groups are positioned at random

isotatic

syndiotactic
chemweb.calpoly.edu

Regioregularity: describing a polymer in which each repeat unit is derived

from the same isomer of the monomer
Example: asymmetry of 3-substituted thiophenes results in three possible
couplings when two monomers are linked between the 2- and the 5-positions
2,5, or headtail (HT), coupling
2,2, or headhead (HH), coupling
5,5, or tailtail (TT), coupling
these three diads can be combined
into four distinct triads

wikepedia

poly(3-hexylthiophene) P3HT having regioregularities of 86, 90, and 96%

Chapter 03

Regiorandom: describing a polymer in which each repeat unit is derived from a

random isomer of the monomer
c) Conformation:
Conformation refers to order that arises from the rotation of molecules about the
single bonds:
thermal fluctuation of the bond length (3%) and bond angle (3-5) are small
at room temperature
rotations around the bonds are well possible
Example: Well flexible macromolecule back-folded chain

Example: solvent polarity effect on chain conformation of DEATG-PPV

diluted solution

concentrated solution

chloroform

methanol

water

Xu et al. J. Phys. Chem. B 114, 1174611752 (2010)

Chapter 03

3.2 Characteristic length scales and sizes

Contour length of a polymer chain is its length at maximum physically possible
extension, but polymer chain is coiled and not fully stretched!

need for a measure of the mean chain size

conformation is fully described with bond vectors li

whole bond vectors is difficult to handle

statistical quantity
a)
Mean-square end-to-end distance Re
Description via bond vectors li which connect the skeleton atoms Ai
Ai-1
li

Ai

Aj-1

rij

lj

Aj

A1

An-1
li

li

A0

An

Not end-to-end vector r but its absolute value is of interest: Time average

r =0

n degree of polymerization

r = r = r r =
2

i , j =1

l j = l + 2 li l j
2
i

i =1

0<i < j

Analog for the distance of the atoms i and j

rij =

i = i +1

2
i

+2

i < i < j

l j

Statistical mean value

n

= l
i =1

2
i

+ 2 li l j
0<i < j

Special case of equal bond length li = l (homopolymer)

R = r
2
e

Chapter 03

= nl + 2 l i l j
2

0<i < j

b)
Radius of gyration Rg
describes chain by the distance vectors si of the skeleton atoms Ai to the center
of mass of the chain (position or radius vector si of the atoms Ai in the center of
mass system of the chain)

Ai-1
Ai

li

rij

si

lj

Aj-1

Aj

sj
A1

An-1
li

li

A0

An

Absolute value of the radius of gyration

n

s = mi s
2

i =0

2
i

m = (1 M ) m s
j =0

i =0

2
i

In case of homopolymers with mi = m it is

1 n 2
s =
s i
n
+
1

i =0
2

Relation of position vectors in the center of mass system with the distance
vectors between atoms and chain

r ij = s j s i

Insert into equation: (Lagrange Theorem)

1
s =
(n + 1) 2
2

0i < j

2
ij

Statistical mean value

R = s
2
g

Chapter 03

1
=
(n + 1) 2

0 i < j

rij2

3.3 Special chain models

a) Freely-jointed chain
fixed length polymer segments are linearly connected
all bond vectors li = l

all bond angles and torsion angles are equiprobable

l i l j = 0 for i j

assumes a polymer as a random walk and neglects any kind of interactions

among monomers end-to-end distance:
n

= nl + 2 l i l j = nl 2 Re = l n
2

0<i < j

Analog to end-to-end distance: rij

= j i l2

Radius of gyration:

l2

1 n+2 2 1 n+2 2
nl =
r
6 n +1
6 n +1

( j i) =

( n + 1)2 0 i < j

Limit of infinite chain (n):

s2 =
with Re = 6.7 n

1 2
r
6

Rg =

Re
6

[ ]

Example: PS (C8H8) with M=104.088

Mw= 1.75 k
n= 17
9k
86
28 k
269
70 k
673
102 k
980
630 k
6053

Rg=

11.2
25.4
44.9
70.9
85.6
212.8

Characteristic ratio of chain with degree of polymerization n (definition):

Cn =

r2
nl 2

with n: CnC
freely-jointed chain: Cn = 1
Chapter 03

C measured in dilute solutions at the -temperature, example:

polyethylene
140C
C=6.8
polyoxyethylen
40C
C=4.0
polystyrene, atactic
34C
C=10.0
polymethylmethacrylate, atactic
4-70C
C=6.9
PMMA, isotactic
27C
C=9.4
PMMA syndiotactic
35C
C=7.2
the more bulky the side groups, the higher C and freely-jointed chain model too
simple
b) Freely-rotating chain
polymer segments make a fixed angle to neighboring units because of specific
chemical bonding: assumption of free bond angles contradicts to the tetrahedra
configuration of the C-atoms
Improvement:

fixed Bond angles i = and fixed bond lengths li=l

all bond rotation angles (torsion angles) are equally likely

Mean angle between neighboring segments l i l i +1 = l cos for i j
2

i-1

li
i

C
H

li+1

C
H

C
H

In general with k segments distance: l i l i + k = l ( cos) l

k

End-to-end distance with degree of polymerization n:

n

n 1

0< i < j

k =1

r 2 = nl 2 + 2l 2 j i = nl 2 + 2l 2 ( n k ) k
r

Characteristic ratio: C n =

Chapter 03

r2
nl 2

1 + 2 1 n
= nl

2
1

(
)

1 + 2 1 n
=

n (1 )2
1

C =

1 + cos
1 cos

Radius of gyration:

1 2 ( n + 2)(1 + )

2 2
2 3
= nl

6
( n + 1)(1 ) ( n + 1)(1 )2 ( n + 1)2 (1 )2 n( n + 1)2 (1 )4

In case of n follows:

s2 =

1 2
r
6

Rg =

Re
6

c) Chain with separable energy

Assumption of free bond rotation angles is too simple, because steric
hindering of the rotation due to side-groups is neglected, and yields wrong
values of C
Improvement:

bond rotation angles get fixed from the bond rotation potential

total energy of chain for all configurations can be separated into

individual contributions from the single bonds
n 1

E{l} = Ei ( i , i ) = E{} = E (1 ... i 1 , i , i +1 ... n )

i =1

Bond rotation angles which are sterically more likely get more probable in the
description with statistical mechanics. In thermal equilibrium, to find a
conformation {} has the probability

P{}d {} =

1
exp( E{}/ (RT ))d {}
Z

with d{}=d1dn
partition function of all conformations

Z = ... d {}exp( E{}/( RT ) )

Selection of cartesian coordinate system for each individual bond with

xi parallel to li
yi in the plane, given by li and li-1
zi perpendicular to this plane
yi
yi

zi
i+1

i-1

li-1

li
i

li+1

li-1

xi
Chapter 03

.
xi
8

Transfer matrix Ti:

Transform vector in i+1 coordinate system into the i-te coordinate system
i

v x

v y = Ti
v
z

vx

vy

vz

i +1

cos i

= sin i cos i

sin i sin i

sin i
cos i cos i

0 vx

sin i v y

cos i v z

cos i sin i

i +1

iterative: bond vector lj in the i-ten coordinate system: ( l j ) i = Ti Ti +1 T j1 l j

Scalar product between bond vectors:
1

l i l j = l i l j (1 0 0) Ti T j1 0 = l i l j Ti T j1

0

statistical mean value (needed to calculate r

l i l j = l i l j Ti T j1

11

mit: Ti T j1 =

i =1

l 2i

11

+ 2 l i l j ):
0< i < j

E{l}
d{l}
RT
E{l}
d{l}
... exp
RT

... Ti ... T j1 exp

Very difficult to calculate exactly, need for simplifications (approximations)

statistical mean value (for fixed i = ):

E( m )
d m
RT
0
= 2
m=i
E( m )
d m
exp
RT
0
2

j1

Ti T j1 = Tm
m=i

j1

Tm exp

only one type of bonds Tm = T and li = l

End-to-end distance:

i =1

0< i < j

0< i < j

r 2 = l 2i + 2 l i l j = nl 2 + 2l 2

2 n 1
r 2 = nl 2 1 + ( n k ) T
n k =1

(T )
j i

11

11

1 0 0

E
=
0
1
0

with identity matrix

0 0 1

Chapter 03

Characteristic ratio:
Cn =

= (E + T )(E T
nl

r2

2T
n

(E T )(E T )

11

Special case of E()=E(-) (Symmetry): sin = 0

sin
cos cos

cos

T = sin cos

cos
0
0

In case of n follows:

C =

1 + cos 1 + cos

1 cos 1 cos

Main contribution of C results from 0 C can reach large values

only bad agreement of measured and calculated values (e.g. calculated
polyethylene with cos( ) = 0.22 yields C=3.4 instead of 6.8 (measured)
d) Chain with discrete isomeric rotational states
RIS (Rotational Isometrie State)
Assumption of independent bond rotation potentials not valid
n 1

E ( , ) E{}
i =1

Interdependence of the bond rotation potentials in the polymer chain not taken
into account, but bond rotation angle at position i depends on the bond rotation
angle at the positions i-1 and i+1
bond rotation potentials have (relative) minima, which are separated from each
other by energy barriers
Example: conformation of n-pentane, resulting from rotation around the two
inner C-C bonds:
a) trans, trans
with 2 = 3 = 0
energetically favorable
head-tail distance 3.6
b) gauche+, gauche+
with 2 = 3 = 120
head-tail distance 2.5
c) gauche+, gauchewith 2 = -3 = 120
suppression of the configuration gauche+, gauche
pentane effect

Chapter 03

10

Sawhorse representation: The spatial orientation are indicated by employing

heavy tapered lines for substituents coming out of the page, normal lines for
substituents in the plane of the page, and dashed lines for substituents going
back behind the plane of the page.
Newman projection: in this representation one views the carbon-carbon bond
directly end-on and represents the two carbon atoms by a circle. Lines going to
the center of the circle represent substituents on the front carbon, and lines going
to the edge of the circle represent substituents on the rear carbon.
Sawhorse representation

Newman projection

Example: conformation of n-pentane

Assumption: 3 rotational isomeric states per bond

energy of the conformation of such chain
n 1

n 1

i =2

i =2

E{} = Ei ( i 1 i ) = E ;i
with
Chapter 03

denoting rotational state of bond i-1

denoting rotational state of bond i
11

Put into Boltzmann factor gives a statistical weight u for the energy E

u ;i = exp( E ;i )

In case of homogeneous chain 3x3 combinations, which can be combined into a

formalism using a 3x3 matrix of statistical weights

g+

t 1

U = g + 1 0 with = exp E

RT

g 1 0
After some lengthily calculation the characteristic ratio is obtained

Cn =

r2
nl

= B1* E + S E S

A1

11

Example: polyethylene at T=140C

RIS model only good for n

e) Kuhn Segment
Adapt concept of freely-jointed chain to real chain by introduction of Kuhn
segment and Kuhn length l'. Each Kuhn segment can be thought of as if they are
freely jointed with each other.
Maximum chain length rmax = n' l '
2
2
2
end-to-end distance r = n' l ' = Cn nl
2
knowing rmax and r allows to calculate n and l

Example: polyethylene n'0.1n and l'8l yields cn=6.8

Chapter 03

12

3.4 Real chain models

a) Gaussian Chain Model
generalization of the freely-jointed chain with polymer segments that are
connected with bond vectors following a Gaussian distribution
3
(l ) =
2
2Nd

3/ 2

3l 2
exp
2
2 Nd

with d 2 = l 2 = d 3l (l )l 2
e.g. Gaussian bead-spring chain with N springs of mean-squared length d*d

rheneas.eng.buffalo.edu

because all directions of bond vectors are equally probable (random walk),
the distribution function of the distanced vectors follows a Gaussian-type
as well

with 4l 2 (l )dl = 1
0

average end-to-end distance

r 2 = l 2 4l 2 (l )dl = Nd 2
0

similar to freely-jointed chain, but d2 replaces l2

However, note that, r = l 4l 2 (l )dl =

0

8 1/ 2
N d = 0.9212 N d
3

which means that average spring length (N=1) is smaller d. Therefore the
average contour length is not Nd.
excluded volume refers to the idea that one part of a long chain molecule
can not occupy space that is already occupied by another part of the same
molecule
excluded volume causes the ends of a polymer chain in a solution to be
further apart (on average) than they would be were there no excluded
volume
Chapter 03

13

b) Worm-like Chain Model

A short-coming of the above models (besides they being phantom chains, i.e. no
self-avoidance) is that there is no intrinsic stiffness. Intuitively, we expect a
bending of the chain to cost energy.
The WLC model envisions an isotropic rod that is continuously flexible; this is
in contrast to the freely-jointed chain model that is flexible only between
discrete segments.
behavior of semi-flexible polymers
Define r(s) as the position as a function
of the relaxed-state contour length, s.
Also shown is the tangent vector t(s),
which is the first derivative of r(s) with
respect to a line segment ds.

Similar to the one-dimensional Heisenberg model for ferromagnets

n 1

H = l i l i +1 with bending modulus = b

i =1

After some calculations with the persistence length Lp=/(kT), the length over
which correlations in the direction of the tangent are lost (mechanical property
quantifying the stiffness of a polymer)
For pieces of the polymer that are shorter than the persistence length, the
molecule behaves rather like a flexible elastic rod, while for pieces of the
polymer that are much longer than the persistence length, the properties can only
be described statistically, like a three-dimensional random walk.
Examples: PS (Mn=98000 g/mol) Lp =15 nm
PVC (Mn=70500 g/mol) Lp =13 nm
Double-helical DNA Lp =50 nm
The ratio of filament length, L, to
persistence length, Lp, showing
flexible
L>>Lp>>a,
semiflexible
LLp>>>a and rigid Lp>>L>>a
regimes.

T.Liverpool Phil. Trans. R. Soc. A 15, 364, 3335-3355

(2006)

Chapter 03

14

 Lp
l
2

r
2
L
l
1
1
exp
end-to-end-distance
p
L

R = r
2
e

l
l
= 2L 1 + exp
L
L p
p
2
p

l
2
2
2

=
=
R
r
l
f
D
with fD=2(x-1+exp(-x))/x being the Debye-function: e
Lp
2
2
2
in the limit l>>Lp: Re = r = 2 L p l
2

a Kuhn segment is equal to twice the persistence length of a worm-like chain

c) Self-Avoiding Chains
The above models all lack the excluded volume interaction between the
monomers.
polymer model with a self-avoiding random walk
monomer-monomer interaction potential assumed to handle the excluded
volume
The self-avoiding random walk (SAW)
on a periodic lattice as a model of a
polymer chain.
first introduced by Flory

average end-to-end distance

Re2 = r 2 = n 2 l 2
with =

3
d +2

with = 0.59 (numerically in 3d)

excluded volume (within mean field theory on d=3 lattice) = 3/5
ideal chain (freely-jointed chain, without self avoidance) = 1/2
Chapter 03

15

d) Blob model
In the 'blob' model, the polymer
chain is made up of n Kuhn lengths
of individual length l. The chain is
assumed to form tangled 'blobs'
between each effective cross-links,
containing ne Kuhn length segments
in each.

polymer chain made up of ne Kuhn lengths

A blobs on a particular chain: A =

n
ne

average end-to-end distance

R = r
2
e

n 2l 2
=
ne

e) compare with measurements

x-ray and neutron scattering give access to radius of gyration Rg
Example: PS in different solvents
polystyrene in benzene
2
(good solvent) Rg = s

1/ 2

n 0.59

polystyrene in cyclohexane
2
(theta solvent) R g = s

1/ 2

n 0.50

from Rubinstein, Colby.

Data compiled by L.J. Fetters, J. Phys. Chem. 1994

chain conformation depends on solvent, thus on interaction polymer-solvent

Chapter 03

16