CHAPTER THREE

The Time-Independent Schrodinger Equation

 Stationary States
 The Potential Step
 The Infinite Square Well
 The Free Particle
 The Finite Square Well
 The Harmonic Oscillator
 The Delta-Function Potential
Wave Mechanics
• Time-dependent Schrödinger equation
In quantum mechanics, the state of any physical system is specified, at each
time “t”, by a state vector |ψ (t) in a Hilbert space H, where |ψ (t) contains all
the needed information about the system. The time evolution of the state
vector |ψ (t) of a system is governed by the time-dependent Schrödinger
equation
……(1)

Where is the Hamiltonian operator corresponding to the total energy of the

system defined as: Hˆ

………(2)
The spectrum of the Hamiltonian, which consists of the entire set of its eigenvalues, is real.
This spectrum can be discrete, continuous, or a mixture of both. In the case of bound states,
the Hamiltonian has a discrete spectrum of values and a continuous spectrum for unbound
states. In the position representation, the time-dependent Schrödinger equation (1) for a
particle of mass “m” moving in a time-dependent potential V(r, t) can be written as follows:

…………(3)

Recall that, according to the probabilistic interpretation of Born, the quantity |ψ(r, t) |2dτ is
the probability of finding the system at time t in the elementary volume surrounding the
point r. Since the total probability is 1, we have 2

………………(4)
• Stationary states: Time-independent potentials
In a large class of problems, the Schrödinger potential V(r,t) has no time dependence and it
is simply a function V(r) of position. In this case the Hamiltonian operator will also be time
independent, and hence the Schrödinger equation will have solutions that are separable, i.e.
solutions that consist of a product of two functions, one depending only on (r) and the other
only on time
…………….. ……(1)

……..(2)

The left side of the above eq. depends only on the variable “”, while the right side depends
only on the variable “t”, since “r” and “t” are independent variable, then both sides must be
equal a quantity which depend on neither “r” nor “t”. Thus, both sides must be equal to the
same separation constant “c”, the right side
 ………(3)

………(4)

…….(5)

This equation is known as the time-independent Schrödinger equation for a particle of

mass m moving in a time-independent potential V(r). Equation (5) can be rewritten as:

…………………….(6)

…………..(7)
A state described by a wave function (7) in which the spatial and temporal parts are
separable is called stationary state, stationary because physical observables of the state are
actually time independent

• Continuity equation
Consider, three-dimensional time dependent Schrödinger equations both for the wave
function ψ(r,t) , and its complex conjugate function ψ*(r,t) . We have

……….(1)

………..(2)

If we multiply the equation (1) by ψ*(r,t) , the equation (2) by ψ(r,t) and subtract the second
from the first,
……(3)
• ……(4)

The result can be written in the form of a continuity equation

……(5)

Which has the familiar form associated with the flow of fluid of density ρ(r,t) and current
density J So, it is reasonable to interpret J as the probability current density, and ρ(r,t) as
the probability density.
Some application to the time-independent Schrödinger equation
• The Potential Step: Unbounded states
An unbound state occurs when the energy is sufficient to take the particle to infinity,
E > V().

fig. 1

Another simple problem consists of a particle that is free everywhere, but beyond a particular
point, say x = 0, the potential increases sharply(i.e. it becomes repulsive or attractive). A
potential of this type is called a potential step as shown in Fig. 2:

Fig.(2)
Two cases:
Case E  V0
The particles are free for x  0. Consider a particle of energy E moving in region in which the potential
energy is the step function. What happened when a particle moving from left to right encounters the
step? The classical answer is simple:
All particles with E < Vo will be reflected back.
All particles with E > Vo will be pass through into zone II.

the particle moves with a speed v = √2E/m. As the particles enter the region x  0, where the
potential now is V = V0, they slowdown to momentum 2m(E-V0) ; they will then conserve
this momentum as they travel to the right.

as example of potential step is a charged particle moves along the axis of

cylindrical electrodes held at different voltages. If the total energy E of
the electron is greater than the work function of the metal, V0 , when the
electron reaches the end of the wire, it will… e
either be reflected or transmitted with some probability.
Wave function splits into two pieces – transmitted part and reflected part.
Fig.(3) Potential step and propagation directions of the incident, reflected, and transmitted
waves, plus their probability densities (x)2 when E V0.

The probabilities of reflection and transmission can be calculated by solving the

Schrödinger equation in each region of space and comparing the amplitudes of
transmitted waves and reflected waves with that of the incident wave.
Schrödinger equation

k  2 mE / 
2 2
in region of space I 1

in region of space II k 22  2m( E  V0 ) /  2

The most general solutions to these two equations are waves:
Since no wave is reflected from the region x  0 to the left, then D = 0 and the complete
wave function is thus given by:

 ( x ) e  it  Ae i ( k1 x  t )  Be  i ( k1 x  t ) x<0
 1
 ( x, t )  
 i t i ( k 2 x  t )

 2 ( x ) e  Ce x≥0

Using the boundary conditions of the wave function at x = 0 to determine the

constants. Since both the wave function and its first derivative are continuous
at x = 0.

 is continuous:  1(0) =  2(0) ⟹ A+B=C

  1 (0)  2 (0) k2
is continuous:  ⟹ A–B= C
x x x k1
The reflection and transmission coefficient, R and T, is
defined by:

To calculate R and T
 ψ

dψ i ( x ) 
i  d ( x)   k1 A
2
J incident   ψ i ( x)

ψ i ( x) i

2m  dx dx 
 m
k1 2 k 2 2
J reflected   B , J transmitted  C
m m
2 2
B k2 C
R 2
, T  2
A k1 A
 A B  C, k1 ( A  B )  k 2 C ;

k1  k 2 2 k1
B A, C  A,
k1  k 2 k1  k 2

( k1  k 2 ) (1   ) 4
2 2
4 k1 k 2
R  T  
k  1   
,
( k1  k 2 ) (1   )  k2
2 2 2 2
1

where  = k2/k1 = √1-V0/E . The sum of R and T is equal

to 1. When E gets smaller and smaller, T also gets smaller
and smaller so that when E = V0 the transmission coefficient
T becomes zero and R = 1. On the other hand, when
E » V0, we have κ = 1-V0/E  1; hence R = 0 and T = 1.
 Case E  V0
The Schrodinger equation is given by:

.(2) Potential step and propagation directions of the incident, reflected, and
transmitted waves, plus their probability densities (x)2 when E  V0.

 d2 
  k  2  ( x )
 dx 2 2
 2 (x ≥ 0)
 
Where k 2 2  2m(V0  E ) /  2 . This equation’s solution is

2 2
 2 ( x )  Ce  k x  De k x (x ≥ 0)
Since the wave function must be finite everywhere, and

since the term e k2 x diverges when x ⟹ , the constant D
has to be zero. Thus, the complete wave function is
 Ae i ( k1 x  t )  Be  i ( k1 x  t )
 x < 0,
 ( x, t )  
Ce i ( k 2 x t ) x≥ 0.
 Thus , the reflected coefficient is given by
2
B k1  k 2
2 2
R  2 1
k1  k 2
2 2
A

The Potential Barrier and Well

Consider a beam of a particles of mass m and energy E approaching a potential

barrier of height V0 and the potential everywhere else is zero.

 0, x  0,


V ( x ) V0 0  x  a,


 0, x a.
Case E  V0 unbound states(continuum states)

We will first consider the case when the energy is greater

than the potential barrier (figure 3).
The wave function will consist of an incident wave, a
reflected wave, and a transmitted wave.
The potentials and the Schrödinger wave equation for the
three regions are as follows: 2
d 1 2m
Region( x  0) V  0 2
 2 E 1  0
dx 
d 2
2
2m
Region(0  x  a ) V  V0 2
 2 ( E  V0 ) 2  0
dx 
d 3
2
2m
Region( x  a ) V  0 2
 2 E 3  0
dx 
 The corresponding solutions are:
 ( x )  Ae ik1x  Be  ik1x , x  0,
 1

 ( x )   2 ( x )  Ce ik 2 x  De  ik 2 x , 0  x  a ,

 3 ( x )  Ee ik1x , x  a,

V(x)
Particle
E
V0

x
0 ɑ

Fig.(3) Potential barrier and propagation directions of the incident, reflected, and transmitted
waves, plus their probability densities (x)2 when E  V0
where 𝑘1=(2𝑚𝐸/ℏ2)1/2 and 𝑘2=(2𝑚(𝐸−𝑉𝑜)/ℏ2) 1/2. The constants B, C, D, and E can be
obtained in terms of A from the boundary conditions:
𝜓(𝑥) and (𝑑𝜓(𝑥)/𝑑𝑥)
must be continuous at 𝑥=0 and 𝑥=a, respectively
The transmission coefficient is thus given by
The Case E  V0: Tunneling: bound states
Now we consider the situation where classically the particle does not
have enough energy to surmount the potential barrier (figure3).
Classically, we would expect total reflection: every particle that arrives
at the barrier (x = 0) will be reflected back; no particle can penetrate
the barrier, where it would have a negative kinetic energy. Quantum
mechanical predictions differ sharply from their classical counterparts,
for the wave function is not zero beyond the barrier. The solutions of
the Schrödinger equation in the three regions yield expression that are
similar to
 ( x )  Ae ik1x  Be  ik1x , x  0,
 1
  ik 2 x
 ( x )   2 ( x )  Ce  De
ik 2 x
, 0  x  a,

 3 ( x )  Ee ik1x , x  a,

 V(x)

V0
Particle
E

+
x
0 ɑ

Fig.(3) Potential barrier and propagation directions of the incident, reflected, and
transmitted waves, plus their probability densities (x)2 when E  V0

Except that  2 ( x )  Ce ik x  De  ik x should be replaced with

2 2

 2 ( x )  Ce k x  De  k x
2 2
  ( x )  Ae ik1x  Be  ik1x , x  0,
 1
  k2 x
 ( x )   2 ( x )  Ce  De
k2 x
, 0  x  a,

 3 ( x )  Ee ik1x , x  a,


where k1  2 mE /  and k 22  2m(V0  E ) /  2 . The behavior

2 2

of the probability density corresponding to this wave function is

expected, as display in Fig.(3), to be oscillatory in the regions x  0
and x  a, and exponentially for 0  x  a. To find the reflection and
transmission coefficients,
2 2
B E
R 2
, T  2
A A
Special cases
1- If 𝐸>𝑉𝑜, and hence 𝜀≫1, the transmission coefficient T becomes
asymptotically equal to unity, 𝑇≅1, and 𝑅≅0. So, at very high energies and
weak potential barrier, the particles would not feel the effect of the barrier; we
have total transmission
2- We also have total transmission when
𝑠𝑖𝑛(𝜆√𝜀−1)=0 or 𝜆√𝜀−1=𝑛𝜋.

, the total transmission, 𝑇(𝜀𝑛)≅1, occurs whenever

𝜀𝑛=𝐸/𝑉𝑜=𝑛2𝜋2ℏ2/(2𝑚𝑎2𝑉𝑜)+1
or whenever the incident energy of the particle is
𝐸𝑛= 𝑛2𝜋2ℏ2/2𝑚𝑎2 with 𝑛=1.2.3
 The Infinite Square Well Potential
The Asymmetric Square Well
Consider a particle of mass m confined to move inside an
infinitely deep asymmetric potential well

V(x) is infinite outside the region 0 ≤ x ≤ a, the wave

function of the particle must be zero outside the boundary.
The solutions only inside the well.
V  V(x) V 

V 0

0 a
Example: A typical diameter of a nucleus is about 10-14m. Use the infinite square
well potential to calculate the transition energy from the first excited state to the
ground state for a proton confined to the nucleus.
Solution:

 2 2 2  2 2 c 2
En  2
n , E1  2 2
 2.0 MeV
2ma 2ma c

The first excited state energy is found to be E2 = 4E1 = 8MeV, and the transition
energy is ΔE =E2 – E1 = 6MeV. This is a reasonable value for proton in the
nucleus.
 Zero-point energy
Generally, the lowest energy in a quantum system is called
the zero point energy.

Why there is no state with zero energy for square well

potential, if the particle has zero energy, it will be at rest
inside the well, and this violates Heisenberg's uncertainty
principle.
Remember Heisenberg uncertainty relation
Particle is confined in box, so x ~ a.
Must be an uncertainty in momentum
Since momentum cannot be zero, minimum
energy must be of order (  p ) 2
 2
E min  
2m 2ma 2
Wave function Probability distribution function

a a
Example (zero point):
The Symmetric Potential Well
What happens if the potential become symmetric?

First, the energy spectrum to remain unaffected by this

translation, since the Hamiltonian is invariant under spatial
translation, as it contains only a kinetic part, it commutes
with the particle's momentum, [H,P] = 0. The energy
spectrum is discrete and nondegenerate.
Second, for symmetric potentials, V(-x) = V(x), the wave
function of bound states must be either even or odd. The
wave function corresponding for above potential can be
written as follows:
 n odd

n even

That is, the wave functions corresponding to odd quantum

numbers n = 1,3,5,….. are symmetric, ψ(-x) = ψ(x), and
those corresponding to even numbers n = 2,4,6,…. are
symmetric, ψ(-x) = -ψ(x).
cos (-x) = cos(x) and sin(-x) = -sin(x)
 The Finite Square Well
The infinite potential is an oversimplification which can
never be realised. A more realistic finite square well.
Consider a particle of mass m moving in the following
symmetric potential:

The two physically interesting cases are E  V 0 and E V 0.

We expect the solutions to yield a continuous doubly-
degenerate energy spectrum for E  V0 and discrete
nondegenerate spectrum for 0  E V0.
Fig.(4) Finite square well potential and propagation directions of the incident,
reflected and transmitted waves when E  V0 and 0  E V0.
  d2   1 
  k
2  ( x )  0 x   a ,
 dx 2 1
 1  
   2 

 d2   1 1 
  k
2  ( x )  0 - a  x  a ,
 dx 2 2
 2  2 
   2 

 d2   1 
  k
2  ( x )  0 x  a ,
 dx 2 1
 3  
   2 

where k1 = √2m (V0-E)/ ħ and k1 = √2mE/ ħ.

Eliminating the physically unacceptable solutions which
grow exponentially for large values of ∣x∣, we can write
the solution to this Schrödinger equation in the regions
x < -a/2 and x> a/2 as follows:
 1
 1 ( x )  Ae k1 x
(x   a ),
2
 k1 x 1
 3 ( x )  De (x  a ).
2
Since the bound state eigenfunctions of symmetric one-
dimensional Hamiltonian are either even or odd under space
inversion, the solutions are then either anti symmetric (odd)
 Ae k1x , x  a / 2


 a ( x )  C sin( k 2 x ),  a / 2  x  a / 2

 De  k1x , x  a / 2,

or symmetric (even)
 Ae k1x , x  a / 2


 s ( x )   B cos(k 2 x ),  a / 2  x  a / 2

 De  k1x , x  a / 2,

To determine the eigenvalues, we need to use the
continuity conditions at x = ± a/2. The continuity of the
logarithmic derivative, (1/ a(x) )d a(x)/dx, of  a(x) at x
= ± a/2 yields
  k2 a 
k 2 cot    k1 . odd parity function

 2 
Similarly, the continuity of (1/ s(𝑥)) d s(𝑥)/d𝑥 at 𝑥 = ± 𝒂/2 gives

 k2 a 
k 2 tan    k1 . even parity function

 2 
Solve these equations to obtain:
nπ
αn  (1,2,3,.....)
2
Since αn2 = m𝒂2En / (2h2) we see that we recover the energy
expression for the infinite well

nπ π 
2 2

αn   En 
2
2
n
2 2 ma
Fig.(5) Graphical solutions for the finit sequare well potential: they are given by the intersection of

R 2   n2 with  n tan n and   n cot n , where  n2  ma 2 En /(2 2 ) and R 2  ma 2Vo /(2 2 )