Chapter 3

QUANTUM MECHANICS

• OBJECTIVES:
• To learn the application of Schrödinger equation to a bound particle and to
learn the quantized nature of the bound particle, its expectation values and
physical significance.
• To understand the tunneling behavior of a particle incident on a potential
barrier.
• To understand the behavior of quantum oscillator.

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An Interpretation of Quantum Mechanics

For an electromagnetic radiation, the probability of finding a photon per unit volume
is related to the amplitude E of the electric field as

PROBABILIT Y
 E2
V

Similarly
 = wave function of a particle
= amplitude of the de Broglie wave
= probability amplitude

Time dependent wave function for a system:

(rj,t) = (rj) e–it
rj is the position vector of the jTH particle in the system.

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 contains all the information about the particle
 → imaginary entity
→ no physical significance
PROBABILITY DENSITY = ||2
||2 → real and positive
→ relative probability per unit volume that the particle will be found at any
given point in the volume
b
Pab = 
a
 2 dx

= area under the probability density

curve from a to b.

Normalization condition:
∞
2
∫  dx = 1
-∞

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Mathematical features of a physically reasonable wave function (x) for a

system:

(i) (x) may be a complex function or a real function, depending on the system;

(ii) (x), must be finite, continuous and single valued everywhere;

(iii) The space derivatives of , must be finite, continuous and single valued

everywhere;

(iv)  must be normalizable.

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• Measurable quantities of the particle (energy, momentum, etc) can be derived from 
• x = expectation value of x (i.e. the average position at which one expects to find the
particle after many measurements)

x    x  dx
−
• The expectation value of any function f(x) associated with the particle is

f ( x)    f (x)  dx

−

Time independent Schrödinger equation

 2 d2
− 2
+ U = E
2 m dx
for a particle of mass m confined to moving along x axis and interacting with its
environment through a potential energy function U(x) and E = total energy of the
system (particle and its environment)
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Particle in an Infinite Potential Well (Particle in a “Box”)

U(x) = 0, for 0 < x < L,

U (x) =  , for x < 0, x > L
U (x) =  , for x < 0, x > L [here (x) = 0 ]

In 0 < x < L, U = 0, the Schrödinger

equation is
d 2 2m
+ E = 0
dx 2 2

d 2 2m E
2
= − k 2
, where k=
dx
(x) = A sin(kx) + B cos(kx) where A and B are constants

At x = 0,  = 0 So, 0 = A sin 0 + B cos 0 or B=0 ,

At x = L ,  = 0 ,
0 = A sin(kL) + B cos(kL) = A sin(kL) + 0 ,

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since A  0 , sin(kL) = 0 .
 k L = n π; ( n = 1, 2, 3, ………..)

2 n λ
k= = or L = n 
λ L 2

2 mE 2 mE
k = ,  kL= L = n
 
Each value of the integer n corresponds to a quantized energy value, En , where

 h2  2
En =  n
2 
n = 1, 2 , 3 …..
8mL 
h2
The lowest allowed energy (n = 1), E1 =
8 m L2
E1 is the ground state energy for the particle in a box
Excited states → n = 2, 3, 4, . . . .
Energies: En → 4E1 , 9E1 , 16E1 , . . . . .
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To find the constant A, apply normalization condition
 2
L
  n  x 
 0 A sin L  dx = 1
2
dx = 1 or 2

−

1 1 − cos 2 n  x  dx
L

 = 1
2
A 2 
0  L 

Solving we get A = 2
L

WAVE FUNCTION n (x) = 2 sin n  x

L L
( )

PROBABILITY DENSITY Pn (x) = 2

L
sin 2
( nx
L
)

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Sketch of (a) wave function, (b) Probability density for a particle in potential
well of infinite height

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A Particle in a Potential Well of Finite Height

A particle is trapped in the well. The total energy E

of the particle-well system is less than U
U(x) = 0 , 0 < x < L,
U (x) = U , x < 0, x > L

• Particle energy E < U ; classically the particle is

permanently bound in the potential well.

• However, according to quantum mechanics, a finite probability exists that the

particle can be found outside the well even if E < U.

• The Schrödinger equation outside the finite well in regions I and III is:

d2 2m 2 2m
where C = 2 ( U − E)
= (U − E) = C 
2


dx2 2

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General solution of the above equation is

( x ) = A e C x + B e − C x
In region I, B = 0; In region III, A = 0;

 = A eCx for x < 0  = B e–C x for x > L

I III

In region II,

d2 2m
II
+ E  = 0
dx2 ћ2 II

k2

II = F sin kx + G cos kx

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A, B, F, G values can be obtained by applying boundary conditions.

ψ I (0) = ψ II (0) ψ II (L ) = ψ III(L )

dψ I dψ II dψ II dψ III
= =
dx x =0 dx x =0
dx x =L dx x =L

WAVE FUNCTIONS PROBABILITY DENSITIES

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Tunneling Through a Potential Energy Barrier

• Consider a particle of energy E

approaching a potential barrier of height
U, (E<U).
• Since E<U, classically the regions II and
III shown in the figure are forbidden to
the particle incident from left.

• But according to quantum mechanics, all regions are accessible to the particle,
regardless of its energy.

• An approximate expression for the transmission coefficient, when T<< 1 is

2 𝑚 𝑈−𝐸
T ≈ e−2CL , where 𝐶 =
ℏ
• Since the particles must be either reflected or transmitted:

R + T =1
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The Simple Harmonic Oscillator

• Consider a particle that is subject to a linear restoring force 𝐹 = −𝑘𝑥, where k is a

constant and x is the position of the particle relative to equilibrium (at equilibrium
position x=0).

• Classically, the potential energy of the system is,

1 2 1
𝑈 = 𝑘𝑥 = 𝑚𝜔2 𝑥 2
2 2

where the angular frequency of vibration is 𝜔 = 𝑘/𝑚.

• The total energy E of the system is,

1 2 1
𝐸 = 𝐾𝑖𝑛𝑒𝑡𝑖𝑐 𝐸𝑛𝑒𝑟𝑔𝑦 + 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = 𝐾 + 𝑈 = 𝑘𝐴 = 𝑚𝜔2 𝐴2
2 2
where A is the amplitude of motion.

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 • A quantum mechanical model for simple harmonic oscillator can be obtained by
1
substituting 𝑈 = 2 𝑚𝜔2 𝑥 2 in Schrödinger equation:

ℏ2 𝑑 2  1
− 2𝑚 𝑑𝑥 2 + 2 𝑚𝜔2 𝑥 2  = 𝐸

• The solution for the above equation is

2
 = 𝐵𝑒 −𝐶𝑥

1
where 𝐶 = 𝑚𝜔/2ℏ and 𝐸 = 2 ℏ𝜔.

• Energy of a state is given by

1
𝐸𝑛 = 𝑛 + 2 ℏ𝜔; 𝑛 = 0, 1, 2 … .

• The state n=0 corresponds to the ground

1
state, whose energy is 𝐸0 = 2 ℏ𝜔

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AN INTERPRETATION OF QUANTUM MECHANICS
QUANTUM MECHANICS
1)
A particle wave function is given + 2
by the equation  (x) = A e–ax
2
−  dx = 1
(A) What is the value of A if this wave function is normalized?
(B) What is the expectation value of x for this particle?

−
+
(A e ) dx
−ax 2
2

+
= 1 2 A
0

2
e −2 ax 2
dx = 1

 e

−2 ax 2
x    * x  dx 2A 2
0
dx = 1

A  (x e 2ax ) dx
− +
− 2 GAUSS’ PROBABILITY INTEGRAL
x = 2
1 

−
2 A  2  = 1

0
x =+ 0 2 2a
 1
x = A2  ( ) dx + A 2  ( ) dx  2 a 4
− 0
A =  16
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Department of Physics - MIT, Manipal 17
AN INTERPRETATION OF QUANTUM MECHANICS
me = 9.11 x 10–31 kg , e = 1.6 x 10 –19 C , h = 6.63 x 10–34 J.s
2) A free electron has a wave function  = A exp [ i (5.00
x 1010 ) x] where x is in meters. Find (a) its de Broglie
wavelength (b) its momentum and (c) its kinetic energy in
electron volts.
(x) = A e ikx
k = 5.00 x 1010 / m

2 / λ = k  λ = 2  / k = 1.26 x 10–10m

p = h / λ = 5.27 x 10–24 kg.m/s

K = p2/ 2m = 1.52 x 10–17J = 95.5 eV

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PARTICLE IN A BOX QUANTUM MECHANICS
mp = 1.67 x 10–27 kg , me = 9.11 x 10–31 kg , h = 6.63 x 10–34 J.s
5) A proton is confined to move in a one-dimensional box of
length L= 0.20 nm. (a) Find the lowest possible energy E1 of
the proton. (b) What is the lowest possible energy E1 for an
electron confined to the same box? (c) Account for the great
difference in results for (a) and (b)

h2
E1 = = 8.22 x 10–22J = 5.13 x 10–3 eV
8 mPL2
h2
E1 = = 1.51 x 10–18J = 9.41 eV
8 m eL 2
The electron has a much higher energy because it is less massive
comparing to the Proton.
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PARTICLE IN A BOX QUANTUM MECHANICS
me = 9.11 x 10–31 kg , e = 1.6 x 10 –19 C , h = 6.63 x 10–34 J.s
6)
(A)Using the simple model of a particle in a box to represent
an atom, estimate the energy [E2–E1] (in eV) required to
raise an electron from the state n= 1 to the state n= 2.
Assume the atom has a radius of r= 0.10 nm and that the
moving electron carries the energy that has been added
to the atom. L = 2 r = 0.20 nm
(B) Atoms may be excited to higher energy states by
absorbing photon energy. Calculate the wavelength λ of
the photon that would cause the transition from the state n
=1 to the state n = 2. hc
2 2  = = 43.8 nm
h n E 2 − E1
En = 2
= (9.4 eV ) n
2

8mL
E2– E1 = (4 – 1) x 9.4 eV = 28.2 eV
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An electron with kinetic energy E = 5.0 eV is
incident on a barrier with thickness L = 0.20 nm
and height U = 10.0 eV.

What is the probability that the electron (a) will tunnel

through the barrier [T]? (b) will be reflected [R]?
U – E = 5 x 1.6 x 10–19J = 8.0 x 10–19J T+R=1
82m(U – E) R=1–T
C = = 1.144 x 1010/ m
h R = 0.990
2 C L = 4.577 T ≈ e–2CL = e–4.577 = 0.0103
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me = 9.11 x 10–31 kg , h = 6.63 x 10–34 J.s , c = 3 x 108 m/s
A quantum simple harmonic oscillator consists of an
electron bound by a restoring force proportional to its
position relative to certain equilibrium point. The
proportionality constant is [k=] 8.99 N/m. What is
the longest wavelength [=λ] of light that can excite the
oscillator ?

hc h k
=  =
 2 m
m
 = 2c = 600 nm
k

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