3C25 Solid State Physics

5. Vibrational Dynamics and Thermal Properties

Atoms always have kinetic energy, and move around their equilibrium positions. Three consequences: (i). Energy can be stored as vibrational energy, and this is reflected in the behaviour of the heat capacity. (ii). Motion contributes to the entropy of the solid, hence free energy, and affects the selection of structure. Vibrations can be transferred through the structure. sound (acoustic) waves. The treatment of vibrations is known as lattice dynamics. Relies upon the properties of the simple harmonic oscillator (SHO).

5.1 Review of the SHO

Traditional example:

5.1.1 Mechanics
Displace mass by u. Restoring force: F = A

Stored potential energy at displacement u:

V =

(iii).

Mass m moving on a frictionless surface, attached to a rigid wall through a massless elastic rod.

Ey Youngs modulus for the rod material. A cross sectional area of rod. l length of rod.

= stress = Ey

So,

u is the strain = l Au F (u ) = E y l

= Ku

Where K is the spring constant. K =

Ey A l

u 0

F (u )du = 1 Ku 2 2

(5.1)

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Solution u = umax cos(t + ) Total energy

2 = 1 Ku max 2

umax = amplitude (t + ) = phase

(5.3)

5.1.2 Thermodynamics
Expose system to a heat bath at temperature T. Equivalent to solving an SHO with a random external driving force. Construct a partition function. Classically:

Mean energy

E =

1 1 du dpH exp ( H k B T ) Z h ln Z = where = 1 / k B T = ln( ) = 1 / = k B T

This is just k B T per degree of freedom: (K.E. and P.E.) So heat capacity is

C=

d E = kB dT

And root mean square displacement is

u2 =

1 1 du dpu 2 exp ( H k B T ) = k B T / k = k B T / m 2 so as T , u 2 . Z h

" #

 



1 2k B T = h K k T = B

1 2

(2mk B T )

1 2





1 h

du exp

dp exp







Ku 2 2k B T



Z=

1 du dp exp ( H k B T ) h p2 2mk B T

u = u

K with angular frequency = m

Newtons 2nd Law:

dp dV = dt du

Hamiltonian

H = T + V = 1 mu 2 + 1 Ku 2 2 2
where p = mu
1 2

Kinetic energy

T = 1 mu 2 2
(5.2)



 

 

(5.4)

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5.1.3 Quantised SHO

1 exp

2 sinh

2k B T

which is the mean number of quanta in the oscillator (Bose-Einstein statistics).

- So we increase number of quanta as T .

Heat capacity

C=

d E dT

k BT

C kB

@A

@A

exp

99

99

B E BCD

BCDB

= kB

k BT

k BT
2

@A

exp

99

99

@A

E CBDB

2 34

8 567

with

= ( n + 1) 2 1 n = exp 1 k BT

E =

ln Z

&% ' ! ( ()0

k BT

% &' %

exp

2k B T

%
(5.5)

n =0

% &'
T
(5.6)

% &'

Now we have

Z=

exp

()0(

! ()0(

()0(

(n + 1 ) En 2 = exp k BT k BT n =0

E CBDB

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5.1.4 Helmholtz Free Energy

F = E TS
We have So for the SHO:

(Gibbs free energy with p = 0)

F = k BT ln Z

F = k BT ln 2 sinh
F
1

S=

(E F )
T k BT

for large T As T , S and u

2

i.e. more displacement from the mean position, more disorder.

k B 1 + ln

@A @A 99 99
The decline in F is a reflection of the increase in entropy with T.

GH GH FF F

E CBDB

2k B T

IPQ

BCDB

(5.7)

IPQI

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3C25 Solid State Physics

5.2 Lattice Dynamics in the Harmon ic Approximation

We aim to relate the vibrations of atoms in a crystalline structure to the properties of an SHO. This will allow us to determine the entropy of the structure. Also will provide phonon picture.

5.2.1 Single Atom in Motion

Consider a linear chain of N atoms of mass m, interacting through a pair potential separation. The minimum P.E. is V0, at nearest neighbour separation a. Separations from atom 0 :

( r ) , r is the

ri = i a
r-2 = 2a r1 = a u0 -1 0 1 2

Label -2

Displace atom labelled 0 from its equilibrium position by a distance u0 to the right :
i =1

i =1

r = ri

i =1

r = ri

r = ri

kinetic energy T = mu

2 4 2 H = V 0 + 1 K E u 0 + 1 mu 0 + O u 0 2 2 4

If we neglect the terms of order u0 , we make the harmonic approximation. Equivalent to an assumption that the displacement u 0 is small. Reduces the Hamiltonian to that of an SHO (See eq. 5.2). This means we can use previous work:

gh

KE where: = m

ipq

or:

E = V0 +

1 1 + exp( k B T ) 1 2

E XX

E = V0 + k B T

1 2

2 0

( )

so

2 4 V (u 0 ) = V0 + 1 K E u 0 + O u 0 2

( )

where K E = 2

N 2

d 2 2 i =1 dr

classically

for quantised cases (See eq. 5.5)

XY

N 2

(ri ) +

d dr

2 u 0 + 1 u0 2

d 2 dr 2

3 + O u 0 (ri )

( )

X`

r = ri

XY

N 2

(ri )

d dr

2 u0 + 1 u 0 2

d 2 dr 2

3 + O u 0 (ri )

( )

X`

Changes in RHS interactions

S R R R T R R R V
i =1

S R R R T R R R V U

change in P.E. is V (u 0 ) V0 =

N /2

( (ri u 0 ) (ri )) +

N/2

( ( ri + u 0 ( ri ))

Changes in LHS interactions

bac

a abc W

a abc W

r = ri

(5.8)

(See eq. 5.4)

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5.2.2 All Atoms in Motion

Again consider linear chain, but now displace all atoms labelled i by ui.

ri + u i

V =
where

1 2

rij = ri rj : separation between atoms i and j. Sum is over all i and j, to avoid double counting.
Pair potential has properties:

and

where

( r ) = (r ) ( r ) = (r ) ( r ) = (r ) d (r ) =
dr
r

and,

(r ) =

[Check these properties with the L-J potential]

V V0 = V =
we have e.g. so,

1 2

ui

(rij ) = 0

by symmetry (cancelation of equal and opposite pairs of terms)

(a ) + ( a ) = 0
V =
Alternatively
1 4

k ij (u i u j )

ij

spring constants, aka coupling constants.

V =

i> j

Compare this with eq. (5.1). Each pair of atoms is effectively joined together by a spring with spring constant kij. It is better to write V as a quadratic form in the displacements:

V =
Hamiltonian is now:

1 2

u i Dij u j
ij

H=

V0 U0
equilibriu m PE

1 2

ui Dij u j +
ij

Change in PE due to displaceme nt

w v u xu y

v u wxu y

Now Taylor expand:

r
ij 2

Use compact notation:

( (r

ij

+ u i u j ) (rij ))

rj + u j

rij + u i u j

d dr 2

(u
ij

u j ) (rij ) +

1 2

(u

u j ) (rij ) + O u i3
2

( )

with

kij = (rij ) ; these are the

1 2

k ij (u i u j )

where the sum is over all pairs.

1 2 i

mui2

KE

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3C25 Solid State Physics

An example:

N = 2 chain with fixed ends.

Approximation: neglect non-nearest neighbour interactions. Label atoms 1 and 2 with displacements u1 and u2.

V = 1 K (u1 ) + 1 K (u1 u 2 ) + 1 K (u 2 ) 2 2 2
2 2

K is the nearest neighbour spring constant.

V = K 2 2u12 + 2u 2 2u1 u 2 2 2 1 u1 K = (u1u 2 ) 1 2 u2 2
1 2

)

T

u i Dij u i

ij

D11 = 2 K
with

D22 = 2 K D12 = D21 = K

(D is deliberately made symmetric)

Transform H to a harmonic oscillator form by diagonalising the D matrix. Define v = u where u and v are N component vectors (elements ui and vi), and is an N N orthogonal matrix. v are linear combinations of the atomic displacements.

( )
We have And But So
i

1 T

definition of an orthogonal matrix. = 1 u = v and u = 1v ui2 = uT u

u T = (1v ) = v T (1 ) = v T u T u = v T 1v = v T v
1 2

Choose such that M is diagonal with diagonal elements i. These are the eigenvalues of M and D, since is an orthogonal matrix. is the matrix of eigenvectors of D.

More importantly:

u i Dij u j = 1 u T Du 2
ij

= 1 v T D1 v 2 = 1 v T Mv 2

where

M = D1

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3C25 Solid State Physics

So, after much effort, we have transformed H to look like the Hamiltonian of N simple harmonic oscillators. The position and velocity coordinates vi and vi are called normal coordinates, which are linear combinations of the atomic coordinates. The oscillatory modes of motion described by these coordinates are called normal modes. They are the natural modes of oscillation of the structure. Each can be excited independently.

e.g.

Eigenvalues

Eigenvectors

=K

= 3K

Alternatively, solve equations of motion: i.e. mu =

dp i H = (Newtons second law) dt u i

Dij u j
j

and by inserting a trial oscillatory displacement pattern u i = Ai cos t we then need to solve

2 mAi =

Dij A j
j 2

which is the same problem of finding the eigenvalues m and eigenvectors Ai of the matrix D. Either way, we can derive the frequency spectrum, which in this example takes the form of two delta functions. (Delta functions are infinitely high, infinitely narrow peaks located at the point where the argument is zero. Main property is Density of states of normal modes

( x x 0 )dx = 1

K 1 = m

3K , 2 = m

1 2

1 2

= K ,3K .

1 1 1 1 2 1 , 2 1

for the N = 2 chain, D = K

The N oscillators have angular frequencies

i =

1 2

Then:

H = V0 +

1 2

i v i2 +

1 2

mv i2

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3C25 Solid State Physics

For N atoms in the 1-d chain, there are N delta functions. For large N , it is useful to introduce a density of states G(), such that G() d is the number of frequencies (i.e. delta functions) lying in the range + d . So, for N = 2 More generally

G ( ) = ( 1 ) + ( 2 ) G()
Shape depends on structure and couplings kij In detail G() is still a set of delta functions. The curve shown measures the density of these along the axis.

Can be extended to 3-d. In the harmonic approximation, H is equivalent to 3N simple harmonic oscillators. There is a density of states G() in 3-d too. What are these normal mode frequencies useful for? Calculating thermodynamic properties, since we know the properties of single oscillators.

2k B T

How do we calculate the frequency spectrum, or density of states?

5.3 Models of normal mode frequen cies 5.3.1 The Einstein Model
Einstein analysed the dynamics of an atom assuming all other atoms were stationary (mean field approximation).

H is combination of Hamiltonians from equation (5.8).

H = V0 +

1 2
i

1 2
i

i.e. single atom in motion case extended to 3-d.

Density of states:

G ( ) = 3 N ( E ) . 3N modes for N atoms in 3-d.

KE All 3N oscillators have frequency E = m

1 2

. Einstein frequency.

2 2 2 K E (u ix + u iy + u iz ) +

F = V 0 + dG ( )k B T ln 2 sinh

ef g

E = V 0 + dG ( ) exp 1 k BT

1 2

fh

ijk i

2 2 2 m(u ix + u iy + u iz )

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