ME6101

Homework 2

Praveen Kumar Yadav

22M1640

September 10, 2023

A zone-boundary phonon mode (K3 ) in an improper ferroelectric material Y M nO3

involves the displacement of atoms, as shown in the figure. In the paraelectric
phase, the phonon mode vibrates in a harmonic potential, while in the ferro-
electric phase, it vibrates in quartic potential (parameters are given below). We
have to solve for the Schrodinger wave equation to find the ground state energy
(E0 ) and the energy of five other levels just above E0 .

h̄2 ∂ 2
" #
− + V ψ = Eψ (1)
2m ∂x2

Harmonic potential parameters

V = K0 + K2 x2
K2 = 1.4494eV /Å2
K0 = 0eV /Å

Quartic potential parameters

V = K0 + K2 x2 + K4 x4
K4 = 1.0342eV /Å4
K2 = −1.4494eV /Å2
K0 = 0eV

1) Solve for harmonic and quartic potential and calculate the spacing between
various energy levels. Choose −1 < x < 1 Angstrom where x denotes the magni-
tude K3 distortion in Angstrom. The effective mass m of mode is m = 266.10
amu. [50 points]
2) For both harmonic and quartic potential, plot the first four eigenvectors.
Discuss the results. [50 points]
import numpy as np
import m a t p l o t l i b . p y p l o t as p l t

h b a r = 6 . 5 8 2 1 1 9 5 6 9 e −16 # eV . s
m = 266.10 # amu
K2 = 1 . 4 4 9 4 # eV/ Angstrom ˆ2
K4 = 1 . 0 3 4 2 # eV/ Angstrom ˆ4

n = 1001
# n e q u a l l y spaced g r i d p o i n t s i n c l u d i n g −1 & 1
x = np . l i n s p a c e ( −1 ,1 , num=n ) # Angstrom
Dx = x [ 1 ] − x [ 0 ] # s p a c i n g between two g r i d p o i n t s

V harmonic = K2 ∗ x ∗∗2 # eV
V q u a r t i c = (−K2 ∗ x ∗∗2 + K4 ∗ x ∗∗ 4) # eV

p l t . p l o t ( x , V harmonic )
plt . plot (x , V quartic )

Figure 1: Potential Field V(x)

HARMONIC POTENTIAL (Paraelectric Phase)

# Write a Hamiltonian matrix and f i n d out i t s e i g e n v a l u e s and e i g e n v e c t o r s

f a c t o r = 1 . 0 3 6 4 2 6 9 7 e −28 # 1 amu∗ ( Angstrom / s ) ˆ 2 = 1 . 0 3 6 4 2 6 9 7 e −28 eV

a = h b a r ∗∗2 / ( 2 ∗m∗Dx∗∗2 ∗ f a c t o r )

H = []

f o r i i n range ( 1 , l e n ( x ) −1):

h = np . z e r o s ( l e n ( x) −2)

i f i == 1 :
h [ i −1] = 2∗ a + V harmonic [ i ]
h [ i ] = −a

e l i f i == l e n ( x ) −2:
h [ i −1] = 2∗ a + V harmonic [ i ]
h [ i −2] = −a
 else :
h [ i −2] = −a
h [ i −1] = 2∗ a + V harmonic [ i ]
h [ i ] = −a

H. append ( h )

H = np . t r a n s p o s e (H)
H = np . a r r a y (H)
#p r i n t (H)

# c a l c u l a t i n g e i g e n e n e r g i e s and c o r r e s p o n d i n g e i g e n s t a t e s
E , v = np . l i n a l g . e i g h (H)
E = E∗1000 # c o n v e r t i n g Eigen e n e r g y v a l u e s i n meV

# p r i n t i n g e n e r g i e s o f f i r s t 10 e i g e n s t a t e s
p r i n t (E [ : 1 0 ] )

#p r i n t ( v )

f o r i i n range ( 1 0 ) :
p r i n t ( ”dE =”, E [ i +1] − E [ i ] )

# u s i n g an a p p r o p r i a t e s c a l i n g f a c t o r f o r p l o t t i n g t he e i g e n s t a t e s
f o r t h e phonon mode
#norm = np . l i n a l g . norm ( v )
v = v ∗10

p l t . f i g u r e ( f i g s i z e =(10 ,6))
p l t . p l o t ( x , V harmonic ∗ 1000)

f o r i i n range ( 6 ) :
c = np . random . rand ( 3 , )
p l t . p l o t ( x [ 1 : − 1 ] , v [ : , i ]+E [ i ] ∗ 1 0 0 0 , c o l o r = c )
p l t . a x h l i n e ( y = E [ i ] ∗ 1 0 0 0 , c o l o r = c , l i n e s t y l e = ’−−’)

p l t . xlim ( [ − 0 . 2 5 , 0 . 2 5 ] )
p l t . ylim ( [ 0 , 5 0 ] )
p l t . x l a b e l ( ” x ( Angstrom ) ” )
p l t . y l a b e l ( ” Energy (meV) ” )
p l t . show ( )

Energy level Energy (meV) Energy Difference (meV)

0 (Ground State) 3.37370 -
1 (1st Excited State) 10.12038 6.74668
2 16.86560 6.74522
3 23.60937 6.74377
4 30.35170 6.74232
5 37.09257 6.74087
6 43.83199 6.73942
7 50.56996 6.73797
8 57.30647 6.73651
9 64.04153 6.73506
From the table it can be seen that the energy difference between consecutive energy lev-
els/eigenstates is almost constant for the harmonic potential. The energy spacing is ap-
proximately 6.74 meV for the given case. Also it can be noticed that the eigenstate/eigen-
vector/eigenwavefunction spills out of the well a bit at the corresponding energy level in
contrast with a classical particle which has zero probability to be found outside the well if
it starts inside the well with certain potential.

Figure 2: First 4 eigenstates shown for the phonon mode

Figure 3: First 20 eigenstates shown for the phonon mode

QUARTIC POTENTIAL (Ferroelectric Phase)
n = 1001
x = np . l i n s p a c e ( −1 ,1 , num=n )
Dx = x [ 1 ] − x [ 0 ]

V q u a r t i c = (−K2 ∗ x ∗∗2 + K4 ∗ x ∗∗ 4) # eV
#p l t . p l o t ( x , V q u a r t i c ∗1000)

# Write a Hamiltonian matrix and f i n d out i t s e i g e n v a l u e s and e i g e n v e c t o r s

f a c t o r = 1 . 0 3 6 4 2 6 9 7 e −28 # 1amu∗ ( / s )ˆ2 = 1.03642697 10−28 eV

a = h b a r ∗∗2 / ( 2 ∗m∗Dx∗∗2 ∗ f a c t o r )

H2 = [ ]

f o r i i n range ( 1 , l e n ( x ) −1):

h = np . z e r o s ( l e n ( x) −2)

i f i == 1 :
h [ i −1] = 2∗ a + V q u a r t i c [ i ]
h [ i ] = −a

e l i f i == l e n ( x ) −2:
h [ i −1] = 2∗ a + V q u a r t i c [ i ]
h [ i −2] = −a

else :
h [ i −2] = −a
h [ i −1] = 2∗ a + V q u a r t i c [ i ]
h [ i ] = −a

H2 . append ( h )

#H = np . t r a n s p o s e (H)
H2 = np . a r r a y (H2)
p r i n t (H2)
p r i n t ( np . shape (H2 ) )

E2 , v2 = np . l i n a l g . e i g h (H2)
E2 = E2∗1000 # c o n v e r t i n g Eigen e n e r g y v a l u e s i n meV
p r i n t ( E2 [ : 1 0 ] )
#p r i n t ( v2 )
f o r i i n range ( 1 0 ) :
p r i n t ( ”dE =”, E2 [ i +1] − E2 [ i ] )

# u s i n g an a p p r o p r i a t e s c a l i n g f a c t o r f o r p l o t t i n g t he e i g e n s t a t e s
f o r t h e phonon mode
norm = np . l i n a l g . norm ( v2 )
v2 = v2 ∗10

p l t . f i g u r e ( f i g s i z e =(10 ,10))
p l t . p l o t ( x , V q u a r t i c ∗1000)
f o r i i n range ( 4 ) :
c = np . random . rand ( 3 , )
p l t . p l o t ( x [ 1 : − 1 ] , v2 [ : , i ]+E2 [ i ] , c o l o r = c )
p l t . a x h l i n e ( y = E2 [ i ] , c o l o r = c , l i n e s t y l e = ’−−’)

p l t . ylim ([ −510 , −490])

p l t . x l a b e l ( ” x ( Angstrom ) ” )
p l t . y l a b e l ( ” Energy (meV) ” )
p l t . show ( )

Energy level Energy (meV) Energy Difference (meV)

0 (Ground State) -503.05725 -
1 (1st Excited State) -503.05725 0.00000
2 -493.55064 9.50661
3 -493.55064 0.00000
4 -484.08082 9.46982
5 -484.08082 0.00000
6 -474.64700 9.43382
7 -474.64700 0.00000
8 -465.24456 9.40244
9 -465.24456 0.00000

For the case of phonon mode in a quartic potential it can be seen that two eigenstates
have the same energies because of the symmetric potential well with two minimas. The
degenerate eigenstates fall in the left and the right hand side of the potential well. These
eigenstates/eigenvectors are confined in the potential well at the corresponding energy but
it also spills out of the well a bit in contrast to a classical particle in a potential well which
can never go out of the well if it starts with a certain potential inside the well.

Figure 4: First 4 eigenstates shown for the phonon mode

 Figure 5: First 150 eigenstates shown for the phonon mode

NOTE

1) In the above problem the value of the eigenstate/eigenvector at the end points x = -
1 & 1 was considered to be zero. The Hamiltonian matrix was solved only for the internal
grid points i.e. 999 points.

2) Programming was done using python.