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2.5
2.6
2.7
2.8
2.9
Radius of gyration
Radius of gyration of an ideal linear chain
conformations
= all states
which can be generated
by rotations around bonds
polymers are loose coils
(Knuel)
continuous change
by statistical movements
parameters:
flexibility of the chain
interactions between monomers on the chain
interactions with surroundings
3
1/2
continuous change
by statistical movements
parameters:
flexibility of the chain
interactions between monomers on the chain
interactions with surroundings
energy in dependence
on the torsion angle
because of sterical hindrance
A2
A0
A3
A1
Ai
Ai-1
Aj-1
An
A4
= 0
Aj
2 = 2 =
=1 =1
A2
A0
A3
A1
Ai
Ai-1
cos
Aj-1
An
= 2 cos
A4
Aj
2 = 2 cos
=1 =1
2 = 2
define:
=1
=1
cos 2 = 2
: characteristic ratio
=1
polymer
8
6
4
100
200
1,4-polybutadiene
polypropylene
poly(dimethylsiloxane)
polyethylene
atactic polystyrene
5.5
6.0
6.8
7.4
9.5
2 2
10
11
Summary
polymer
1,4-polybutadiene
polypropylene
poly(dimethylsiloxane)
polyethylene
atactic polystyrene
()
5.5
6.0
6.8
7.4
9.5
9.9
11
13
14
18
: degree of polymerization
: monomer length
1/2
1
2
12
assumptions:
1. all bond lengths and bond angles fixed
2. all torsion angles < are equally probable,
i.e. the potential = .
= 2 cos
13
=1
=1
=+1
2 = 2 = = + 2 +
=1 =1
=1
=1
= 2 + 2 (cos ) + (cos )
=1
=+1
= 2 + 2 (cos ) + (cos )
=1
=1
k = i-j.
j = 1 k = i-1.
j = i-1 k = 1.
=1
k = j-i.
j = i+1 k = 1.
j = n k = n-i.
14
=1
=1
=1
(cos ) + (cos )
2
2
2cos
1+
1 cos
1 + cos
1 cos
2 (cos ) = 2
=1 =1
cos
1 cos
15
2.
the potential ( )
is not constant
1 + cos 1 + cos
=
1 + cos 1 + cos
( )
( )
0 cos exp
( )
0 exp
16
Ri R j
Rj
cm
R i R cm
R cm
Ri
with
=1
=1
17
=1
=1
=1
1
1
1
2
= 2 +
1
1
2
= 2 2 + = 2 2
=1 =1
=1 =1
1 1
1
2
2
2
=
2 2
2
=1 =1
2
2
=1 =1
1
=
2
2
=1 =1
1
= 2
=1 =
alternative definition of
radius of gyration (useful
for scattering experiments!)
18
1
2
= 2
0 and
=
= ( )2
2
2
( )2
2
= 2 ( ) =
2 2
3
0
2
6
2 3
=
2 2 3
2
=
6
19