Department of physics, NTNU Nanoparticle and polymer physics I, Solution - Exercise 1 p.

1
FY8201 / TFY8 Nanoparticle and polymer physics I
SOLUTION of EXERCISE 1
Eq. (x.x) refers to version AM24nov05 of lecture notes: Nanoparticle and polymer physics.
Equations pertinent to this exercise you will nd in Ch. 2.3.
A) The Rouse chain consists of N segments (beads) connected by N 1 segment vectors (springs).
We assume that 1) there are no other forces than the spring force, 2) the end beads are free, 3) all
springs obey Hookes law with Hookes constant H. Relative to the laboratory coordinate system
the position of bead is r

( = 1, 2, . . . N), and we dene r

0
= r
1
and r
N+1
= r
N
. Note that for
the one-dimensional chain the coordinates r

are scalars and not vectors.

Newtons law for bead no. reads:
m r

= H [(r
+1
r

) (r

r
1
)] (1)
We change the coordinate system from the laboratory system to cm-system with origo in the center
of mass r
cm
=

N
=1
r

/N. The coordinates in cm-system then aren R

= r

r
cm
and Eq. (1)
transforms to
m

R

= H [(R
+1
R

) (R

R
1
)] = H [R
+1
2R

+ R
1
] , (2)
or on vector form
m

R = H

R, where

A

1 1
1 2 1
1 2 1
.
.
.
1 1

. (3)
Note that matrix

A

is not the Rouse matrix. Also note that in this one-dimensional chain the
components of the vector

R = [R
1
, R
2
, . . . , R
N
] are scalars, but for a three-dimensional chain the
components are vectors.
The essence now is to rewrite Eq. (2) to be expressed by the segment vectors Q

= R
+1
R

( =
1, 2, . . . (N 1)). From the above dened r
0
= r
1
and r
N+1
= r
N
follows Q
0
= 0 and Q
N
= 0, and
we obtain
m

Q

= H [Q
+1
+ Q
1
2Q

] , (4)
or on vector form
m

Q = H

Q, where

A=

2 1
1 2 1
1 2 1
.
.
.
1 2

. (5)
Now the (N 1) (N 1)-matrix

A is precisely the Rouse-matrix, see Eq. (2.46). We have thus
easily obtained the Rouse matrix from Newtons law using the relative coordinates

Q.
B) Let = |Q| be the length of each segment. In the limit N the length L = N of the chain
must be kept constant, so 0. It is thus natural to expand in a series in . Coordinate x is used
as space coordinate:
R

R(x), R
1
R(x ). (6)
Taylor expansion to fourth order yields
R
1
= R(x ) = R(x)
R
x
+
1
2

2
R
x
2

2

1
6

3
R
x
3

3
+
1
24

4
R
x
4

4
+ (7)
Department of physics, NTNU Nanoparticle and polymer physics I, Solution - Exercise 1 p.2
Using this, Eq. (2) may be expressed
m

2
R
t
2
= H
2

2
R
x
2
+

2
12

4
R
x
4
+
_
. (8)
In the limit 0 we obtain the wave equation of zeroth order with the wave velocity c given by
c
2
= H
2
/m:

2
R
t
2
=
H
2
m


2
R
x
2
. (9)
C) In the continuous case (N ) the eigenvectors of the Rouse matrix are trivial. A vibrating
rod has the quantization properties (standing wave in the rod with xed endpoints: a whole number
of /2 along the rod):
j

2
= L, j = 1, 2, . . . . (10)
The eigenvalues of the matrix

A are given by

A

Q = a
j

Q. From Eq. (5) and using the continuous
standing wave solution Q exp{i(t kx)} we obtain

A

Q =
m
H

Q =
m
H

Q. (11)
Further, using the relation c
2
= H
2
/m, expressing the wave velocity c =

2
, using Eq. (10) and
= L/N, the eigenvalues a
j
can be expressed
a
j
=
m
H

2
=
2
_

c
_
2
=
2
_
2

_
2
=

2
j
2
N
2
. (12)
This is precisely the same as obtained taking the limit N of the eigenvalues of the Rouse
matrix in the discrete case: Holding L constant we obtain for the Rouse eigenvalues:
a
j
= lim
N
4 sin
2
_
j
2N
_
= lim
0
4 sin
2
_
j
2L
_
=

2
j
2

2
L
2
=

2
j
2
N
2
. (13)
D) In the discrete case (nite N) the most direct method would be to nd the N eigenvalues by
zeroing the determinant of the equation, but we do an alternative approach.
The eigenvalues represent the characteristic resonance modes. Each resonance mode j = 1, 2, 3,
is a longitudinal standing wave where all beads oscillate with the same frequency
j
but dierent
phases. A standing wave in a chain of length L may be represented by
f
j
(x, t) = Asin
_
2
2L
j x
_
cos
j
t. (14)
The function is fullling the end constriction f
j
(0, t) = f
j
(L, t) = 0, c.f. Eq. (10). For our discrete
chain the position x is given by bead number and L N = total no. of beads. The function
f
j
(x, t) is represented by connector Q

(should strictly be denoted Q

,j
= connector Q

in mode
j), given by
Q

= Asin
_
2
2N
j
_
cos
j
t. (15)
Using complex notation: sin =
1
2i
(e
i
e
i
) and for simplicity dening n =
2
2N
j, we obtain
Q

= B
_
e
in
e
in
_
e
int
. (16)
Inserting this expression in Eq. (4), we obtain:
m

Q

= H [Q
+1
+ Q
1
2Q

]
m(
2
n
)(e
in
e
in
) = H
_
(e
i(+1)n
e
i(+1)n
) + (e
i(1)n
e
i(1)n
) 2(e
in
e
in
)
_

m
2
n
H
(e
in
e
in
) = e
in
(e
in
+ e
in
) e
in
(e
in
+ e
in
) 2(e
in
e
in
)
a
n
(e
in
e
in
) = (e
in
e
in
)(e
in
+ e
in
) 2(e
in
e
in
)
a
n
= (e
in
+ e
in
) 2 , (17)
Department of physics, NTNU Nanoparticle and polymer physics I, Solution - Exercise 1 p.3
where we have dened a
n
=
m
2
n
H
, determined to be
a
n
= 2 (e
in
+ e
in
) = 2 2 cos(in) = 4
1 cos(in)
2
= 4 sin
2
_
n
2
_
, (18)
or, more directly
a
n
= (e
in
2 + e
in
) =
_
e
in/2
+ e
in/2
_
2
= 4
_
e
in/2
+ e
in/2
2i
_
2
= 4 sin
2
_
n
2
_
. (19)
Now n =
2
2N
j and the conclusion is that the eigenvalues of the Rouse matrix fullls
a
j
= 4 sin
2
_
j
2N
_
Comments:
1) Note that the for the continous vibration we do not accept dispertion: After disturbing the
system all frequency components will move with the same velocity c =
_
H/m. This is not
the case for the discrete case, then the wave velocity equals
n
/k where
2
=
H
m
sin
2
_
j
2N
_
. The
continuous limit corresponds to limiting to the linear part of the dispertion relation of the rod: We
study waves with wavelengths much larger than the distance .
2) You may perhaps not like that the wave velocity c
2
=
2
H/m seems to diverge to zero when
0. Remember that the mass and the spring constant are given by m = and H = F/,
where is mass per length unit and F is the force (stretch) of the spring. From these variables we
obtain c
2
= F/, as for a macroscopic spring.
3) Both free and constricted boundary conditions yield the same quantization conditions for the
nite chain, and the same eigenvalues of the Rouse matrix. For constricted ends the amplitudes are
zero at the ends, but for free ends the relative amplitudes are zero at the ends. When additionally
the dierential equation is the same for the amplitude and the relative amplitude, we surely obtain
the same quantization conditions. (For periodic boundary conditions it is somewhat dierent, as
the eigenfrequency has doble degeneration.)
NPP lf01.tex AM. 23.10.09