1 Schrdinger Wave Equation

1.1 Time-independent Schrdinger Equation

The form of the wave function is assumed to be

ψ = ei(kx−ωt) . (1)

Differentiating Eq. 1 twice with respect to x, we will get

d2 ψ
= −k 2 ψ. (2)
dx2

P
K= (3)
h̄
d2 ψ P2
2
=− 2ψ (4)
dx h̄
d2 ψ
−h̄2 = P 2ψ (5)
dx2

−h̄2 d2 ψ P 2ψ
2
= (6)
2m dx 2m
The total energy of a given particle is given by

E = K.E + P.E
1
E = mv 2 + V
2
P2
E = +V P = mv; P 2 = m2 v 2 ; (7)
2m

P 2ψ
Eψ = +Vψ (8)
2m

−h̄2 d2 ψ
Eψ = +Vψ (9)
2m dx2

1.2 Time-dependent Schrdinger equation

Differentiating Eq. 1 with respect to t, we get
dψ
= −iωψ (10)
dt

E = h̄ω (11)

Eψ = h̄ωψ (12)

1
 Multiply Eq. 12 by − h̄i

−i
Eψ = −iωψ
h̄
dψ
= (13)
dt

h̄ dψ
Eψ = −
i dt
dψ
= ih̄ (14)
dt

dψ −h̄2 d2 ψ
ih̄ = +Vψ (15)
dt 2m dx2

2 Particle in a box
2.1 Particle in a square well potential
Consider the Fig. 2.1. From the figure, we can see that the potential (V(x)) is
zero in between 0 and L and infinity beyond 0 and L. Since this potential profile
is looking like a ’well’ and it is having infinite potential beyond the well shaped
region, it is called as infinite potential well. (If the potential is finite beyond the
well shaped region, it can be called as a finite potential well.). A particle in the
infinite potential well can move freely with the region which is limited by 0 and
L and can not penetrate into the region beyond 0 and L. Thus the probability
of finding the particle beyond the region 0 and L is zero. Physically, this type
of potential well can be approximated as a rigid box.
The potential profile of the above mentioned problem is given by

V (x) = 0 f or 0 < x < L,

V (x) = ∞ otherwise. (16)

2
 Since the quantum mechanical particle can not exist beyond 0 and L, the
wave function becomes zero in that region:

ψ(x) = 0 f or x<0
and
ψ(x) = 0 f or x>L (17)

The time independent Schrödinger wave equation for a quantum mechanics

particle is given by Eq. 9 and can be rewritten for a pa as

2mE d2 ψ
ψ= . (18)
h̄ dx2
A possible solution for Eq. 18 can be written as

ψ(x) = A sin(kx) + B cos(kx), (19)

where A and B are the coefficients which quantize the contribution of sin(kx)
and cos(kx) respectively, to the wave function ψ.

Boundary condition:1 At x=0, ψ(x) = 0. Substituting x=0 in Eq. 19, we

get
ψ(0) = B cos(0) = 0. (20)
Since cos(0) = 1, we can conclude that B should be zero.

Boundary condition: 2 At x=L, ψ(L) = 0. Substitute x=0 and B=0 in Eq.

19, we get

ψ(0) = A sin(kL) = 0. (21)

Since A can not be equal to zero, sin(kL) = 0 must be zero in Eq. 21 and it
becomes

sin(kL) = 0. (22)
The equation 22 will be satisfied only if kL = nπ.
We can write that
nπ
k= , (23)
L
where n=1, 2, 3,....
Now Eq. 18 becomes

2mE ∂2
− A sin(kx) = A sin(kx). (24)
h̄2 ∂x2
After simplification, 24 becomes

3
 2mE
− = k2
h̄2
h̄2 2
E= k (25)
2m
Substituting the value of k in Eq. 25, we get

h̄2 π 2 2
n . (26)
2mL2
Eq. 26 gives the expression for energy of a particle in an infinite square well
potential. In Eq. 26, n can take any integer value and only the integer value.
Thus the energy E is discrete and not continuous.