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Lecture2 PDF
Lecture2 PDF
Chain.
Freely-Jointed Chain.
n n n n
R = u i u j = u i u j
i =1 j =1 i =1 j =1
n
n
n
n
2
2
R = u i u j = u i + u i u j
2
i =1 j =1
i =1
i , j =1,
i j
but for the freely-jointed chain u i u j = 0 for i j , and therefore
R
=
i=1
2
u i = Nl 2 = Ll , L = Nl , where L is the contour length
of the chain
R 2 = N 1/ 2l , R L
Freely-Jointed Chain.
R
R 2 = N 1/ 2l , R L
We see that:
- the conformation of the ideal chain is far from rectilinear;
- the ideal chain forms an entangled coil;
- the trajectory of the chain is equivalent to the trajectory of a
Brownian particle.
C
C
As before
=
i =1 j =1
n
2
ui u j = ui +
i =1
2
2
u i = b , but now u i u j 0
ui u j ,
i , j =1,
i j
= Nb + b
i , j =1
i j
i+1
i
cos i ,i +1 = cos
i+2
cos i ,i +2 = cos 2
= Nb + 2b
N N i
i =1 k =1
cos i ,i +k = Nb + 2b
cos
2 1 + cos
Nb + 2 Nb
= Nb
1 cos
1 cos
2
(where k = j - i)
N N i
k
cos
i =1 k =1
1 + cos
=N b
1 cos
1/ 2
Thus, within the model with a fixed valency angle we once again
get an entangled coil: the typical size of the coil is once again
proportional to the square root of the contour length of the chain.
This result is a universal feature of the ideal chains regardless of
the particular flexibility model.
For < 90o the value of R is larger than for the freely-jointed
chain, while for > 90o it is smaller.
kb
k
cos i ,i + k = (cos ) = exp ( k ln cos ) = exp
=
b ln cos
= exp s l , l = b ln cos
u (0 )u (s ) = exp s l
L 2
R R
l = Ll
l
We get once again the same result: the size of the coil R is
proportional to the square root of the chain length L.
2
(for large L)
1 + cos
l l = ln cos
1 cos
2.2
~
l/l
2.1
2.0
1.9
/4
Normally, the Kuhn segment length is larger than the typical size
of a monomer unit characterized either by d or by the contour
length per one unit l0.
3/ 2
Ld
(Ll )
3/ 2
1/ 2
d
=
L
d
l
3/ 2
r0 =
mi ri = ri
NM i =1
N i =1
where the second equation is vaid for a homopolymer whose
monomer units all have a same mass.
Moreover, gyration radius of a coil is defined by
1 N
2 1 N 2
2
S =
mi (ri r0 ) = (ri r0 )
NM i =1
N i =1
The value of gyration radius can be measured directly in the light
scattering experiments, which will be discussed in one of the
subsequent lections.
For an ideal coil one can show that
1 2
1
2
S = R = Ll
6
6
3/
2
3
R
2
PN R = (2 Nl 3) exp
2
2
Nl
This is the reason why the ideal polymer coil is also often called
Gaussian coil.
Note, the normaliztion condition, and the fact that the dependences
of different coordinates are factorisable:
3
PN R d R = 1
()
()
()
()
3/
2
3
R
2
PN R = (2 Nl 3) exp
2
2
Nl
()
3/ 2
3R 2
2
2
PN R = (2 Nl 3) exp
R
2
2
Nl
()
3/ 2
3R 2
exp
2 R2