PHY-1203

(Physics-II)

6th Chapter: Quantum Mechanics

Wave Function
 In quantum mechanics, various atomic parameters are described with the help of wave
function ψ. Function determining the state of a system is called state function or wave
function. The probability that a particle will be found at a given place in space at a given
instant of time is characterized by the function ψ (x, y, z, ). It is called the wave function.

Physical Significance of ψ
We have assumed that the wave associated with a particle in motion is represented by
the wave function ψ (x, y, z, t). A wave function is a complex quantity and is not an
observable quantity. Therefore, it has no direct physical significance. Since it is a
complex quantity, it may be expressed in the form

ψ ( x, y, z , t ) = a + ib …………………..(i)

where, a and b are real functions of the variables (x, y, z, t) and i = √-1.
 The complex conjugate of ψ which is denoted by ψ* is given by

……………..(ii)
ψ ( x, y, z , t ) = a − ib
*

Multiplying equ. (i) and (ii), we have

……………..(iii)
ψ ( x, y, z , t )ψ ( x, y, z, t ) = a + b
* 2 2

On the left hand side of the equ. (iii) the product is denoted by

2
P = ψ ( x, y, z , t )ψ ( x, y, z , t ) = ψ ( x, y, z , t )
*

2
∴ ψ ( x, y , z , t ) = a + b 2 2 ……………..(iv)
Thus the only quantity having a physical meaning is the product of ψ and ψ* which
is real and positive if ψ ≠ 0 and hence observable. Its positive square root is denoted
by ψ ( x, y , z , t ) and it is called modulus of ψ.
2
The quantity ψ ( x, y , z , t ) is called the probability density. The probability of
2
finding a particle in a volume dxdydz is ψ dxdydz.
2
A large value of ψ means the strong probability of the particle’s presence. A small
2
value of ψ means the slight possibility of the particle’s presence.

Further since the particle is certainly to be found somewhere in space

2
∫∫∫ ψ dxdydz = 1
the triple integral expending over all possible values of x, y, z.
 Orthogonal and Normalized Wave Function
If the product of a wave function ψ1(x) and the complex conjugate ψ2*(x)
of a function ψ2(x) vanishes when integrated with respect to x over the interval
a≤x≤b that is
b

∫ψ
*
2 ( x)ψ ( x) dx = 0
1
a
then ψ1(x) and ψ2(x) are said to be orthogonal in the interval (a,b).

∫ψ
*
If
k ( x)ψ k ( x) dx = 1
a

then the functions are said to be normalized in the interval (a,b).

Schrödinger Time-dependent Equation
The quantity that characterizes the de-Broglie waves called the wave
function. Let us assume that ψ is specified in the x direction by
− iω ( t − x v ) ……………..(i)
ψ = Ae
If υ is the frequency then ω = 2πυ and v = υλ

−2πi (ν t − x λ ) ……………..(ii)
∴ ψ = Ae
Let E be the total energy and P the momentum of the particle. Then E = hυ
and λ = h/P. Substituting these in equ.(ii)
−2πi
( E t −P x) ……………..(iii)
ψ = Ae h

Equ. (iii) is a mathematical description of the wave equivalent of an unrestricted

particle of total energy E and momentum P moving in the +x-direction.
At speeds small compared with that of light, the total energy E of a particle is the sum of
its kinetic energy P2/2m and its potential energy V. V is, in general, a function of x and t.
2
P ……………..(iv)
∴ E= +V
2m
Multiplying both sides of equ. (vi) by ψ, we get

P 2ψ ……………..(v)
Eψ = + Vψ
2m
Differentiating equation (iii) twice with respect to x, we get

−2πi
∂ψ 2πiP ( E t −P x)
= . Ae h
∂x h
∂ ψ 4π i P
2 2 2 2 −2πi
( E t −P x) ∂ψ
2
4π P 2 2
∴ 2
= 2
. Ae h
or , =− ψ
∂x h ∂x 2
h 2
 h 2
∂ 2
ψ ……………..(vi)
∴ Pψ =− 2
2

4π ∂x 2
Differentiating equ. (iii) once with respect to t, we get
−2πi
∂ψ 2πiE ( E t −P x)
=− . Ae h
∂t h
∂ψ 2πiE
or , =− ψ
∂t h
∂ψ h
∴ Eψ = − ……………..(vii)
2π i ∂t
Substituting these values of P2ψ and Eψ in equ. (v), we have

h ∂ψ h 2 ∂ 2ψ
− =− 2 + Vψ
2π i ∂t 8π m ∂x 2
 ih ∂ψ h ∂ψ 2 2
∴ =− 2 + Vψ ……………..(viii)
2π ∂t 8π m ∂x 2

Equation (viii) represents the time-dependent form of Schrödinger's wave equation in

one-dimension.

In three dimensions, the time-dependent form of Schrödinger's equation is

ih ∂ψ h ∂ψ ∂ψ ∂ψ 2 2 2 2
= − 2 ( 2 + 2 + 2 ) + Vψ
2π ∂t 8π m ∂x ∂y ∂z
ih ∂ψ h 2
∴ = − 2 ∇ ψ + Vψ
2

2π ∂t 8π m
2 2 2
where, ∇ 2 =
∂ ∂ ∂
2
+ 2+ 2 is the Laplacian operator.
∂x ∂y ∂z
Schrödinger Time-independent Equation
Schrodinger’s equation is a differential equation capable of describing the
motion of an electron. The one-dimensional wave function ψ may be written
in the form
−2πi (νt − x λ )
ψ = Ae ……………..(i)
Differentiating equ.(i) twice with respect to x, we get
∂ψ 2π i
=( ). Ae − 2πi (νt − x λ )
∂x λ
∂ψ
2
4π i2 2
− 2πi (νt − x λ ) 4π 2
∴ = ( 2 ). Ae =− 2 ψ
∂x 2
λ λ
∂ ψ 4π
2 2
or , + 2 ψ =0 ……………..(ii)
∂x 2
λ
At speeds small compared with that of light, the total energy E of a particle is the sum
of its kinetic energy P2/2m and its potential energy V. V is, in general, a function of x
and t.
P2
E= +V or , P 2 = 2mE − 2mV
2m
∴ P = 2m(( E − V )
Now, de-Broglie wave-length is given by

h h h
λ= = =
mv P 2m( E − V )
Substituting this value of λ in equation (ii), we get

∂ψ2
4π 2

2
+ ψ =0
∂x [h 2m( E − V ) ] 2
 ∂ 2ψ 4π 2
2
+ ψ =0
∂x [h 2m( E − V ) ] 2

∂ ψ 8π m
2 2
……………..(iii)
∴ 2
+ 2 ( E − V )ψ = 0
∂x h
It is known as time-independent Schrödinger's wave equation in one-dimension.

For three dimensional motion of an electron, this equation becomes

∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2 m
2
+ 2 + 2 + 2 ( E − V )ψ = 0
∂x ∂y ∂z h
2
8π m
or , ∇ ψ + 2 ( E − V )ψ = 0
2

h
2 2 2
where, ∇ 2 =
∂ ∂ ∂
2
+ 2+ 2 is the Laplacian operator.
∂x ∂y ∂z
Applications of Schrödinger's Equation
(Particle in a Box)
 Consider a particle moving inside a box along the X-direction. The particle is bouncing
back and forth between the walls of the box. The box has insurmountable potential
barriers at x = 0 and x = L, so that the particle has no chance of penetrating them. The
particle has a mass m and its position at any instant is given by 0 < x < L.

The potential energy V of the particle is infinite

on both sides of the box. The potential energy V
of the particle can be assumed to be zero
between x = 0 and x = L. Thus we have the
potential function

V ( x) = 0 for 0〈 x〈 L
V ( x) = ∞ for x ≤ 0
V ( x) = ∞ for x ≥ L Fig. 1: A one-dimensional potential box
The one-dimensional Schrodinger’s equation of the electron occupying nth state is given by

d ψ n 2m
2

+ 2 ( En − V )ψ n = 0 ………………(i)
dx 2

Within the box V = 0, hence the one-dimensional Schrodinger’s equation becomes

d 2ψ n 2m
+ 2 Enψ n = 0 ………………(ii)
dx 2

2mEn
Putting k2 = 2
, the equation becomes

d 2ψ n
+ k 2
ψn = 0 ………………(iii)
dx 2

The general solution of this equation is

ψ n ( x) = A sin kx + B cos kx ………………(iv)

where A and B are constant and are determined by applying the boundary conditions
Since the electron is bound inside the crystal of length L, the electron’s wave
function has to satisfy the following boundary conditions, i.e.

(i ) ψ n ( x) = 0 at x = 0
Hence, from equation (4) we have

0 = A sin 0 + B cos 0 ∴B=0

(ii ) ψ n ( x) = 0 at x = L
Hence, from equation (4) we have

0 = A sin kL + 0 cos kL or , A sin kL = 0

Since, A ≠ 0, sin kL = 0

nπ
∴ kL = nπ or , k = where, n is an integer
L
 Thus, the wave function becomes
nπ
ψ n ( x) = A sin( ) x ………………(v)
L
Thus the allowed energy value can be obtained as
2k 2  2 nπ 2 n 2π 2  2 n 2 h 2 ……………(vi)
En = = ( ) = =
2m 2m L 2mL 2
8mL2
The lowest energy of the particle is obtained from this equation by putting n = 1 as

h2 2
E1 = = or , E n = n E1
8mL 2

For each value of n, there is an energy level

and the corresponding wave function is given
by equation (v). Each value of En is called an
eigen value and the corresponding ψn is called
eigen function. Thus inside the box, the
particle can only have discrete energy values
Fig. 2: Schematic representation of energy level
specified by equ. (vi).
 The value of the constant A could be determined by normalizing the wave function. It is certain
that the particle is somewhere inside the box. Hence for normalized wave function, the total
probability that the particle is somewhere in the box must be unity, i.e.
L L
2
∫ψ ( x)ψ n ( x)dx = 1 or , ∫ ψ n ( x) dx = 1
*
n
0 0

L
nπx A2
L
2πnx
0r , ∫ A sin2 2
dx = 1
0
L
0r ,
2 0∫ (1 − cos
L
)dx = 1

A2 L 2 nπ x L 2L
0r , [x − sin ]0 = 1 or , A =1
2 2π n L 2
2
∴A =
L
2 nπ x
Thus the normalized wave function is given by ψ n ( x) = sin
L L
 The normalized wave function ψ1, ψ2 and ψ3 are plotted in Fig. 3

Fig. 3: The wave function for n = 1, 2 and 3

It can be shown that the wave function ψ1 has two nodes at x = 0 and x = L, ψ2 has three
nodes at x = 0, x = L/2 and x = L and ψ3 has four nodes at x = 0, x = L/3, x = 2L/3 and x = L.
Consequently, the wave function ψn will have (n+1) nodes.
Q. For a particle in a box show that

(1) n = 0 state is not allowed.

(2) Energy is quantized.
(1) n = 0 state is not allowed
We know the wave function of a particle in a box is given by

nπ x
ψ n = A sin
L
n2h2
and energy E =
n
8mL2

If n = 0, we get

ψn = 0 and En = 0
i.e., there is no wave function and energy state. Hence n = 0 state is not allowed.
(2) Energy is quantized :
We know the wave energy of the particle in a box is given by

n2h2
En =
8mL2
h2 4h 2 9h 2
A few energy levels are E1 = , E2 = ,E =
3
and so on.
8mL2 8mL 2
8mL2
For each value of n, energy state is discrete. So energy is quantized.

The energy of a particle in a box is

(i) inversely proportional to the square of the length of the box and
(ii) inversely proportional to the mass of the particle
 Linear Harmonic Oscillator
 Consider a particle of mass m executing simple harmonic motion along the
x-direction. The restoring force on the particle is F and is directed towards
the mean position. F depends on the displacement x.

∴ F = −k x where, k is the force constant

d 2x
or , m 2 + k x = 0 ………………..(i)
dt
The general equation of SHM is given by

d 2x
2
+ω x = 0
2 ………………..(ii)
dt
k
Comparing equ. (i) and (ii) ω =
2

m
or , k = mω 2 = m(2πυ ) 2 = 4π 2 mυ 2
The potential energy of the harmonic oscillator is given by
x x
1 2
V = − ∫ F dx = ∫ k x dx = k x
0 0
2
1
∴ V = × 4π 2 mυ 2 × x 2 = 2π 2 mυ 2 x 2 ………………..(iii)
2
This is the potential energy of the harmonic oscillator.
The Schrödinger equation is given by

d 2ψ 2m
2
+ 2 ( E − V )ψ = 0 ………………..(iv)
dx 
Substituting the value of V = 1 k x 2 in equation (ii) we get
2

d ψ 2m
2
1 2
2
+ 2 ( E − kx )ψ = 0 ………………..(v)
dx  2
 d ψ 2m
2
or , 2
+ 2 ( E − 2π mυ x )ψ = 0
2 2 2

dx 
d 2ψ  2mE 4π 2 m 2υ 2 x 2 
or , ψ = 0
………………..(vi)
2
+ 2 − 2
dx    
2E
Taking λ=
 (2πυ )
2π mυ
and α = 2


2π mυ 2E 2mE
∴ α λ =(
2
)× = 2
  (2πυ ) 
Substituting these values in equ. (vi)

d 2ψ
2
+ (α 2
λ − α x )ψ = 0
4 2 ………………..(vii)
dx
Dividing by α2
1 d 2ψ
+ ( λ − α x )ψ = 0
2 2 ………………..(viii)
α dx
2 2

Taking new variable dy

y =α x ∴ =α
dx
dψ dψ dy dψ
∴ = . =α
dx dy dx dy
2
d ψ d dψ d dψ dy d dψ
2
= ( ) = ( ) = ( )α
dx dx dx dy dx dx dy dx
2 2
d ψ d dψ 2 d ψ
∴ 2 = (α )α = α
dx dy dy dy 2
 1 d 2ψ d 2ψ
or , 2 2 = 2
α dx dy
Substituting these values in equation (viii), we have

dψ2

2
+ ( λ − y 2
)ψ = 0 ………………..(ix)
dy
This is the Schrödinger's equation in terms of y and λ for a linear harmonic oscillator.

The solution of the equation (ix) can be written as

− y2 2
ψ = φ ( y )e ………………..(x)

where φ (y) is a function of y that remains to be found.

Differentiating equation (x) twice with respect to y, we get

dψ 2
2 
2 d φ
2
dφ 
= e −y
 2 − 2y + ( y − 1)φ 
2 ………………..(xi)
dy 2  dy dy 
Substituting the values of ψ and d2ψ/dy2 in equation (ix), we have

d 2φ dφ
2
− 2y + (λ − 1)φ = 0 ………………..(xii)
dy dy
which is the differential equation that φ obeys.

The Hermite’s differential equation is given

d 2φ dφ
2
− 2y + 2n φ = 0 ………………..(xiii)
dy dy
Comparing equations (xii) and (xiii), we have

λ − 1 = 2n where, n = 0, 1, 2, 3 ……

2E
But λ=
 (2πυ )
Equating these two equations, we have the energy eigen values of harmonic oscillator

2E
2n + 1 =
 (2πυ )
1
or , E = (n + ) (2πυ )
2
1
∴ E = (n + )hυ
2
1
In general E n = ( n + ) hυ
2
It means that the energy of the harmonic oscillator has discrete values depending upon
the values of υ. The energy levels here are evently spaced as in Fig. 1.
 1
We note that, when n = 0, E0 = hυ which is the lowest value of energy of the
2
oscillator. This value is called the zero point energy.

Wave Functions
Each wave function ψn consists of a polynomial Hn(y) (called a Hermite
2
polynomial), the exponential factor e − y 2 and a numerical coefficient which is
needed for ψn to meet the normalization condition
∞

∫ψ
−∞
n dy = 1
The general formula for the nth wave function is
2mυ 1 4 n −1 2 − y2
ψn = ( ) (2 n!) H n ( y )e 2


Problems