UNIT V

CHAPTER 1

QUANTUM MECHANICS

Introduction:

Physical world

Macroscopic world Microscopic world

Classical mechanics Quantum mechanics

In the late seventeen century, Isaac Newton discovered classical mechanics, the law of
motion of macroscopic objects.
In the early twentieth century, physicists found that classical mechanics does not
correctly describe the behavior of very small particles such as the electrons nuclei
(protons & neutrons etc.) and molecules. The behavior of such particles is described by a
set of laws called Quantum mechanics.
I.e. Classical mechanics applies only to macroscopic particles. For microscopic
“particles” .We require a new form of mechanics, called Quantum mechanics.

Classical mechanics:
 Classical mechanics deals with the motion and behavior of macroscopic
particles.
Ex: Motion of planets.

 Classical mechanics is expressed in the language of un-probabilities, certainties.

Quantum mechanics:
 Quantum mechanics deals with the motion and behavior of microscopic
particles
Ex: Motion of Electrons
 Quantum mechanics is expressed in the language of probabilities, not certain.

DUAL NATURE OF MATTER

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de-Broglie hypothesis:
According to de-Broglie hypothesis, every moving particle has always associated with a
wave. The particle is controlled by this wave in every aspect.
The wave associated with moving particle of matter (like electrons, protons etc) are
known as matter wave or pilot waves or de-Broglie waves.

Figure .1 Motion of particle (Electron)

If a particle of mass m moving with velocity v, then the wavelength of matter wave is
given by
h
λ=
mv

Where
h Planck’s constant,
m mass of particle,
vvelocity of the particle
Derivation of de – Broglie’s wave length:
According to Planck’s quantum theory of radiation (light) the energy of photon is given
by
E = hν (1 )
Where h -> Planck’s constant,

ν -> frequency of radiation

According to Einstein’s energy-mass relation, the energy of photon is given by
2
E = 𝑚𝑐 (2)

Where m-> mass of photon

C-> velocity of light or photon

Figure .2. Motion of photon

From the above equations (1) and (2); we can write
𝑐
h𝜈 = m𝑐 2 [∵ C = νλ and ν = 𝜆 ]

hc
= mc2
λ

h
= mc
λ

h h
λ= = (3)
mc p

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Where p = mc is the momentum of photon having mass m and travelling with velocity c.
de - Broglie suggested that equation (3 )can be applied both for photos and material
particles. If m is mass of the particle and v is the velocity of the particle, then
Momentum (p) = mv

h
de – Broglie wave length λ = (4)
mv

This equation represents that the de-Broglie wave length associated with a particle and
also known as de –Broglie’s wave equation.

OTHER FORMS OF de –Broglie’s WAVE LENGTH:

1. de –Broglie’s wave length in terms of energy

If m is mass of the particle and v is the velocity of the particle, then the kinetic energy of
the particle;
1
E = 2 mv 2
Multiplying by ‘m’ on both sides; we get
1
m E = 2 m2 v 2
2 m E = m2 v 2

(Or) m v = √2 m E

h 𝒉
de – Broglie wave length λ = = (5)
mv √2 m E

2. de –Broglie’s wave length in terms of voltage

If a charged particle of charge ‘q’ is accelerated through a potential difference
‘v’, then
E=qv (6)
1
Also we know that the K.E of the particle E = 2 mv 2 (7)
Equating equations ( 7 )and (6 ) we get
1
mv 2 = q v
2
Multiplying by ‘m’ on both sides we get
1
m2 v 2 = m q v
2
m2 v 2 = 2 𝑚 𝑞 𝑣
m v = √2 m q v (8)
Substituting equation 8 in equation 4 , we get

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 h h
de – Broglie wave length λ = = (9)
mv √2 m q v

3.de –Broglie’s wave length for electron

Substituting the values of m, q and h in equation 9 we get

6.626 X 10−34 JS
λ=
√2 X9.1 X 10−31 KgX1.6 X10−19 C X V

12.27 X 10−10 m
= [ 1 A0 = 10−10 m ]
√V

12.27
λ = A0
√V

This equation represents the de – Broglie wave length associated with an electron.

4.Wave velocity:
We know that
E= h𝜈 and E = m𝑐 2
h𝜈= m𝑐 2
mc2
ν=
h
The wave velocity is given by
ω=νλ
mc2 h
ω= .
h mv
c2
∴ ω=
V
Thus matter waves travel faster than velocity of light.

Properties of de-Broglie waves:

The following are the properties of matter waves.

1. The de-Broglie wavelength of particle of mass ( m) moving with a velocity (V) is
h
given by λ =
mv
If v = 0, λ  and if v, λ0.
This implies that matter waves are associated with material particles only if they are in
motion
2. Lesser the velocity of the particle, larger the wave length associated with it.
3. Smaller the mass of the particle, the greater the length associated with it.
4. The matter wave of particle is independent of charge (or) nature of the particle.
5. de-Broglie waves are pilot waves. The word, pilot means that these waves pilot (or)
guide the particle.
c2
6. Matter waves travel faster than velocity of light, i.e., ω = .
V
7. Mater waves are not electromagnetic waves.
8. The wave nature of matter introduces an uncertainty in the location of the position of
the particle because a wave cannot be set exactly at this position (or) at that position.
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9. de-Broglie waves are called probability waves. The amplitude of the wave tells us
about the probability of finding particle in space at a particular instant. Large wave
amplitude means large probability of finding the particle at that position.

NOTE:

1. Mention an application of matter waves?

A. The electron microscope is an application of matter waves, associated with electrons
2. Why cannot we experience the existence of matter waves in our day to day life?
h
A. λ = , if m is large,  will be small, thus the wave length will be very small,
mv
compared to the size of the particle, hence it is not observable.

Heisenberg uncertainty principle:

In 1927, Heisenberg proposed a very interesting principle, which is direct consequence

of the dual nature of matter, known as uncertainty principle.

According to Heisenberg uncertainty principle, it is impossible to determine accurately

and simultaneously the values of position and momentum of a particle at any time.
If Δx is the error (uncertainty) in measuring position, Δp is the error (uncertainty) in
measuring momentum; then according to this principle

h
Δx.Δp ≥
4π

h h
NOTE: Similarly such relations are ΔE. Δt ≥ and ΔJ. Δθ ≥ 4π, Where E and
4π
t are the uncertainties in determining the energy and time, while J and θ are
uncertainties in determining the angular momentum and angle.

Application of uncertainty principle:

1.It is verified Nonexistence of Electrons inside the nucleus.
2. It is also verified Existence of protons and neutrons inside the nucleus
3. It is calculated binding energy of electron in an atom
4. It is also calculated Mass of  -meson
5. Emitted radiation of excited atom is confirmed by this principle.

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Physical significance of wave function:

Wave function: - it is a mathematical tool used in quantum mechanics to describe any

physical system, and it is denoted by ‘ψ’.

 It is variable quantity i.e., associated with a moving particle at any position (x,y,z)
and at any time t and it relates probability of a finding the particle at that point
and at that time.
 It must be well behaved, that is single valued and continuous everywhere.
 It usually complex quantity and individually it has no meaning.
 To explain it, Max born suggested a new idea about the physical significance of ψ
which is generally accepted now a days.
 According Max born ψ ψ*=|𝜓|2 is a real and positive, it has physical meaning.
It represents the probability of finding the particle in the state ψ.

 Since the wave function is a complex

quantity, it may be expressed in the form of
Ψ(x,y,z) = (a+ib)
Where a,b are real function of the
variables (x,y,z,t) and i=√−1.
 The complex conjugate of ψ is given by
Ψ* (x,y,z) = (a-ib)
Multiplying the above two
equations, we have
Ψ Ψ*= (a+ib) (a-ib) = a2+b2
According to Max born

P= Ψ Ψ*= |ψ(x,y,z) |2 = a2+b2

Thus the product of ψ and ψ * is real and positive if ψ≠0 and is known as probability
density of the particle associated with the de-Broglie wave

 The probability of finding the particle in a volume dv=dx.dy.dz is given by

Probability (p) = |𝜓|2dx dy dz

 For the total probability of finding the particle somewhere is (space).

P = ∭|𝜓|2 dx dy dz =1
 A wave function ψ satisfying the above relation is called a normalized wave
function.
 For motion of a particle in one dimensional, the quantity
Pdx = |𝜓|2dx is the probability of finding the particle over a small distance dx
at position x.

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Schrodinger wave equation:-

Definition: - The equation that describes the wave nature

of a particle in mathematical form is known as
Schrodinger’s wave equation.

There are two types of Schrodinger wave equations they

are

1) Time independent wave equation and

2) Time dependent wave equation

Schrodinger one dimensional Time independent wave equation :-

Let us consider a particle of mass m moving with a velocity v. Let 𝜑 be the wave
function of a particle along X-direction at any time (as shown in figure).

The classical differential equation of wave motion is given by

∂2 ψ 1 ∂2 ψ
= (1)
∂x2 v2 ∂t2

The solution for equation (1) is assumed to be

ψ = ψ0 e−iωt (2)

Where ψ0 is the amplitude of the wave at any point..

Differentiating equation (2) partially with respect to‘t’; we get

∂ψ
= ψ0 e−iωt × (- iω ) (3)
∂t

Differentiating once again equation (3) partially with respect to‘t’; we get

∂2 ψ
= ψ0 e−iωt × (- iω ) x (- iω )
∂t2

= ψ0 e−iωt ( -ω2 ) [ from eq (2)]

= - ω2 ψ (4)

Substituting equation (4) in (1) we get

∂2 ψ 1
= (-ω2 ψ)
∂x2 v2

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 ω2
=- ψ (5)
v2

But ω =2π𝑣 = 2π v⁄λ (v= 𝑣λ and v=v⁄λ )

ω 2π
(or) = → (6)
v λ

Substituting equation (6) in (5), we get

∂2 ψ 4π2 ψ
+ =0 (7)
∂x2 λ2

This is the classical wave equation in terms of wavelength.

Schrodinger connected the expression for the de Broglie wave the length in to the
classical wave equation in terms of wavelength for a moving a particle and obtained a
new wave equation.

We know that debroglie wavelength is given by

h
λ= → (8)
mv

Substituting equation (8) in (7), we get

∂2ψ 4π2 m2 v2
+ ψ=0 →(9)
∂x2 h2
1
If E is the total energy of a particle, ‘V’ is the potential energy and mv2 is the kinetic
2
energy; then

Total energy (E) =P.E+K.E

1
E =V+ 2 mv2

1
(Or) E-V= 2mv2

2(E-V) = mv2

Multiplying by ‘m’ on both sides in the above equation, we get

2m (E-V) = m2 v2 → (10)

Substituting equation (10) in (9) we get

∂2 ψ 8π2 m
+ → (11)
(E-V) ψ=0
∂x2 h2

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 ∂2 ψ 2m
Or + (E-V) ψ=0 (12)
∂x2 ħ2
h
Where ħ =
is called plank’s reduced constant.
2π
This equation is known as Schrodinger time independent one-dimensional wave equation.

Note:
For 3dimensional:
∂2 ψ ∂2 ψ ∂2 ψ 8π2 m
+ + + (E-V)
∂x2 ∂y2 ∂z2 h2
ψ=0
8π2 m
Or ∇2 ψ+ (E-V) ψ=0
h2

∂2 ∂2 ∂2
∇2 = + + is called Laplace
∂x2 ∂y2 ∂z2
operator.

Time dependent wave equation:

Let us consider a particle of mass m moving with a velocity v. Let ψ be the wave
function of a particle along x-direction at any time (as shown in figure).
The classical differential equation of wave motion is given by
∂2 ψ 1 ∂2 ψ
= (1)
∂x2 v2 ∂t2
The solution for equation (1) is assumed to be

ψ = ψ0 e−iωt (2)

Where ψ0 is the amplitude of the wave at any point..

Differentiating equation (2) partially with respect to‘t’; we get

∂ψ
= ψ0 e−iωt × (- iω )
∂t

= −iωψ (3)
ω
But E = hv = h
2𝜋

h ω
= ω ( ω= 2𝜋v and v = )
2𝜋 2𝜋

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 ∴E=ħω
E
And ω = (4)
ħ
Substituting equation (4) in eq (3), we get

∂ψ E
=−i ψ
∂t ħ
E
= iħ
ψ
∂ψ
Eψ=iħ (5)
∂t

Substituting equation (5) in Schrodinger time independent one-dimensional wave

equation, we get

∂2 ψ 2m
+ ħ2 (E-V) ψ = 0 (6)
∂x2

∂2 ψ 2m
+ ħ2 (E ψ -V ψ) =0
∂x2

∂2 ψ 2m ∂ψ
+ ħ2 (i ħ -V ψ) =0
∂x2 ∂t

ħ2
Multiplying 2𝑚 on both sides, we get

ħ2 ∂2 ψ 2m ħ2 ∂ψ
+ ħ2 . 2𝑚 (i ħ - V ψ) =0
2𝑚 ∂x2 ∂t

ħ2 ∂2 ψ ∂ψ
+ (i ħ - V ψ) =0
2𝑚 ∂x2 ∂t

ħ2 ∂2 ψ ∂ψ
- V ψ = −i ħ
2𝑚 ∂x2 ∂t

ħ2 ∂2 ψ ∂ψ
- +V ψ = i ħ
2𝑚 ∂x2 ∂t

This equation is known as Schrodinger time dependent one-dimensional wave equation.

Or H ψ = Eψ

−ħ2 ∂2
Where H = + V is called Hamilton operator
2𝑚 ∂x2
∂
E = i ħ ∂t is called energy operator.

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Particle in one dimensional box or well:
 Let us consider a particle of mass ‘m’ moving with velocity ‘v’ along x-direction
and is confined between to infinite potential rigid walls, so that the particle has no
chance of escaping from them. Therefore, the particle bounces back and forth
between two walls as shown in fig.
 Let the potential energy of electron inside the box is
constant and can be taken as zero for simplicity.
 From fig , we consider two regions :
(i) Outside the box
(ii) Inside the box
Outside the box:
The particle cannot exist outside and on the walls of
the box; therefore the probability of finding the
electron outside the wall is zero and the potential
energy is∞.

i.e., ψ(x)=0 When x≤ 0 and x≥ 𝑙

V(x) = ∞

Inside the box:

The particle exists inside the box; therefore the probability of finding the electron
inside the box is no equal zero and the potential energy is zero.
ψ(x)≠0
i.e., When x>0 and x< 𝑙
V(x) = 0
 To calculate the probability of finding particle within the box , let us consider one
dimensional time independent Schrödinger wave equation

d2 ψ 8π2 m
i.e., + (E-V(x)) ψ=0 (1)
dx2 h2

Inside the box, the potential energy V(x) = 0

Therefore, equation (1) becomes
d2 ψ 8π2 mE
+ ψ=0
dx2 h2
d2 ψ
(Or) + k2 ψ=0 (2)
dx2
8π2 mE
Where k 2 = (3)
h2
Equation (2) is a second order differential equation; therefore it should have
solution with two arbitrary constants.
∴ The solution for equation (2) is given by
Ψ(x) = ASin Kx+BCos Kx (4)
Where A and B are called as arbitrary constants, which can be found by applying the
boundary conditions.
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Boundary Condition at x=0:
At x = 0, the probability of finding the electron is zero, i.e., ψ(x) =0
Equation (4) becomes
O = A Sin K (0) + B Cos K (0)
O=0+B
(5)
∴B = 0

Boundary Condition at x=l:

At x = l, the probability of finding the electron is zero, i.e., ψ(x) =0

Equation (4) becomes
O = A Sin K (l) + B Cos K (l)
O = A Sin K (l) + (0) Cos K (l) [ Since B = 0]
A Sin K (l) = 0
Since A≠ 0; Sin K (l) = 0 (6)

We know that, Sin 𝑛𝜋 = 0 (7)

Comparing these two equations, we can write

K (l) = 𝑛𝜋
𝑛𝜋
K= (8)
𝑙
n2 π2
k2 = (9)
𝑙2

Substituting the values of ‘B’ and ‘K’ in equation (4),

Equation (4) becomes
𝑛𝜋𝑥
Ψn(x) = ASin (10)
𝑙

This equation represents the wave function associated with moving free electron
inside the box.

Normalization of the wave function: it is the process by which the probability (P) of
finding the particle or electron inside the box can be done.

The total probability that the particle is somewhere in the box must be unity
𝑙
i.e ., P= ∫0 |ψn (x)|2 (11)

[Since the particle present inside the box between the length 0 to l, then the limits are
chosen between 0 to l ]
Substituting equation (10) in equation (11), we get

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 𝑙 𝑛𝜋𝑥
P= ∫0 A2 Sin2 dx = 1
𝑙
𝑙 𝑛𝜋𝑥
A2 ∫0 Sin2 dx = 1
𝑙
1−Cos2x
[Since Sin2 x = ]
2

1−𝐶𝑜𝑠2𝑛𝜋𝑥
𝑙 2
A 2
∫0 𝑙
= 1
𝑆𝑖𝑛𝑛𝜋𝑥
𝐶𝑜𝑠𝑛𝜋𝑥
[Since ∫ 𝑙
= 𝑙
𝑛𝜋 ]
𝑙

A2 𝑙 1−𝐶𝑜𝑠2𝑛𝜋𝑥
2
∫0 𝑙
𝑑𝑥 = 1

A2 𝑙 1−𝐶𝑜𝑠2𝑛𝜋𝑥
2
∫0 𝑙
𝑑𝑥 = 1

A2 𝑙 𝑙 𝐶𝑜𝑠2𝑛𝜋𝑥
2
[∫0 𝑑𝑥 − ∫0 𝑙
𝑑𝑥 ] =1
𝑆𝑖𝑛2𝑛𝜋𝑙
A2 A2 𝑙
[𝑙 ] − [ 2𝑛𝜋 ]=1 (12)
2 2
𝑙

Since Sin n𝜋 = 0, Sin 2n𝜋 is also= 0

Equation (13) can be written as

A2
[𝑙] = 1
2

2
A2=
𝑙

2 (13)
A= √
𝑙

Substituting the values of ‘A’ in equation (10),

2 𝑛𝜋𝑥
Ψn(x) = √ Sin (14)
𝑙 𝑙

Each value of wave function is known as Eigen function .The various Eigen functions of
an electron enclosed in a1D box as shown in fig.

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Case 1: If n=1, then Ψ1(x) has two nodes at x=0 and x= l.
𝑙
Case 2: If n=2, then Ψ2(x) has three nodes at x=0 and x= 𝑎𝑛𝑑 𝑥 =l.
2

𝑙 2𝑙
Case 3: If n=3, then Ψ3(x) has four nodes at x=0 and x= 𝑎𝑛𝑑 𝑥 = 𝑎𝑛𝑑 𝑥 =l.
3 3
Therefore Ψn(x) has (n+1) nodes.

Probability of the location of the particle:

The probability of finding a particle over a small distance dx at x is given by

P(x) dx = |ψn (x)|2 dx

2 𝑛𝜋𝑥
P(x) dx= Sin2
𝑙 𝑙

Thus, the probability density for one dimensional motion

is

2 𝑛𝜋𝑥
P(x) = Sin2
𝑙 𝑙

The probability density is maximum when

𝑛𝜋𝑥 𝜋 3𝜋 5𝜋
= , ,
𝑙 2 2 2

𝑙 3𝑙 5𝑙
x= , , …….
2𝑛 2𝑛 2𝑛
𝑙
Case 1: If n=1, then the probability of position of the particle is at x= 2
𝑙 3𝑙
Case 2: If n=2 then the probability of position of the particle is at x= 4 and 4 .
𝑙 3𝑙 5𝑙
Case 3: If n=3, then the probability of position of the particle is at x= and and .
6 6 6
these positions are shown in fig.

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Energy of the Particle:

From the equations (3) & (9)

8π2 mE
k2 = (3)
h2

n2 π2
k2 = (9)
𝑙2
8π2 mE n2 π2
=
h2 𝑙2

n2 h2
En= (15)
8m𝑙 2

This is an expression for the energy of the particle.

Each value of En is known as Eigen value.

The various Eigen values of an electron enclosed in a 1D box as shown in fig

2
h
Case 1: If n=1, then E1= 2.
8m𝑙
2
4h
Case 2: If n=2, then then E2= 2 = 4E1
8m𝑙
2
9h
Case 3: If n=3, then E3= 2 = 9E1 and so on. Therefore, energy levels of electron are
8m𝑙
discrete.

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