Module 2: Quantum mechanics

Duality of matter waves/Wave particle dualism/de Broglie hypothesis

Interference, diffraction of light – Light is considered as a wave.
Compton effect, Photoelectric effect - Light is considered as a particle.
De Broglie hypothesis – Matter waves
ℎ
De Broglie wavelength 𝜆 = 𝑚𝑣

De Broglie wavelength of an accelerated electron

For an electron of charge ‘e’ accelerated under a potential difference of V, energy acquired is
eV.
If m is the mass and v is the velocity of the electron, then the energy equation is:
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𝑒𝑉 = 2 mv2 …………………………………… (1)

If p is the momentum of the electron, then p = mv

Squaring both sides, we get
p2= m2v2
𝑝2
Or 𝑚 𝑣 2 = , Using this in (1), we get:
𝑚

𝑝2
𝑒𝑉 = 2𝑚 or 𝑝2 = 2𝑚𝑒𝑉

Hence, 𝑝 = √2𝑚𝑒𝑉
ℎ
Following de Broglie's hypothesis, we get 𝜆 = 𝑝

ℎ 1 ℎ
𝜆= = ( )
√2𝑚𝑒𝑉 √ 𝑉 √2𝑚𝑒
1 6.63×10−34 1.226×10−9
𝜆= (√2×9.11×10−31 )= m
√𝑉 ×1.602×10−19 √𝑉

Heisenberg’s uncertainty principle

Statement: “In any simultaneous determination of the position & momentum of a particle, the
product of the corresponding uncertainties inherently present in the measurement is equal to or
ℎ
greater than .
4𝜋

The uncertainty relations are:

ℎ ℎ ℎ
∆𝑥∆𝑝 ≥ 4𝜋, ∆𝐸∆𝑡 ≥ 4𝜋 , ∆𝐿∆𝜃 ≥ 4𝜋

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where x is position, p is momentum, E is energy, t is time, L is angular momentum is angular
displacement.

Nonexistence of electron inside the nucleus – Application of HUP

𝑃2
The energy E of a body can be expressed as 𝐸 = 2𝑚 ……. (1)

m is the mass of the body, p is the momentum

ℎ
Heisenberg’s uncertainty principle is ∆𝑥∆𝑝 ≥ 4𝜋
ℎ
Hence, ∆𝑝 ≥ 4𝜋∆𝑥 ………… (2)

W.K.T. the typical value of diameter of nucleus is of the order of 10-14 m.

This can be taken to be approximately the maximum space of confinement.
Thus, if an electron is to exist inside the nucleus, then the uncertainty in its position ∆𝑥 must
not exceed this value.
Allowing maximum uncertainty value, we get ∆𝑥  10-14 m.
Substituting the values of h and ∆𝑥 in (2), we get
6.63 × 10−34
∆𝑝𝑥 ≥
4𝜋 × 10−14
∆𝑝𝑥 ≥ 0.5 × 10-20 Ns which is the uncertainty in the momentum of the electron.
Then the momentum of the electron must at least be equal to the uncertainty in the
momentum, we can state:
𝑝𝑥 ≥ 0.5 × 10-20Ns ……………… (3)
We know that the mass of the electron is m = 9.11 ×10-31 kg.
Now, by making use of the inequality (3) in equation (1), we can say that, in order that the
electron may exist within the nucleus, its energy E must be such that:
(0.5 × 10−20 )2
𝐸≥
2 × 9.11 × 10−31
𝐸 ≥ 1.37210−11 J
Expressing in eV, we get
𝐸 ≥ 1.37210−11 6.241018 eV or 𝐸 ≥ 85 𝑀𝑒𝑉
An electron may exist inside the nucleus, then its energy must be greater than or equal to 85
MeV.
But the experimental investigation on beta decay reveals that the kinetic energy of the beta
particles is of the order of 3 to 4 MeV.

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This clearly indicates that electrons cannot exist within the nucleus.
Wave function
In quantum mechanics, it is postulated that there exists a function determined by the physical
situation.
The function is called wave function.
It is also postulated to contain all possible information about the system. Hence it is also
called a state function.
The wave function may vary w.r.t. both the position coordinates of the physical system &
time.
It is called total wave function represented as .
If the wave function has variation only with position & not with time, it is represented as .
The total wave function can be represented by the equation:
Ψ = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡)
Where A is a constant,  is the angular frequency of the wave.
The physical significance of the wave function could be realized through its probabilistic
nature which is well depicted in quantum mechanics in terms of probability density.
If we consider a single particle & is the wave function associated with the particle, then
||2 is the probability per unit volume that the particle will be found at the given point.
Physical significance of the wave function & normalization
Let  be a volume inside which a particle is known to be present, but where exactly the
particle is situated inside  is not known.

Then the probability of finding the particle in a certain element of volume d of  is ||2 d.
For these reasons, ||2 is called probability density.
If we are certain to the extent that the particle is present in a particular region or space of
𝜏
volume , then as per the statistical rule, ∫0 ||2 𝑑𝜏 = 1

This is because a value 1 for probability means, it is clearly a certainty. However, in the above
case, if we are not at all certain about locating the particle in a finite volume anywhere in space,
then the expectation will become limited to the extent that 'it exists somewhere in space'.

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Then the lower and upper limits will be - to + respectively. Therefore, the above equation
+
becomes ∫- ||2 𝑑𝜏 = 1
+
But in most cases, the result of evaluation of ∫- ||2 𝑑𝜏 = 1 will not be unity but involves
a constant that existed in the equation for .
However, the actual result of whatever is obtained is equated to unity and the value of the
constant is determined.
It is then substituted in the equation for  which becomes the working equation for the wave
function. This process is called normalization.
Properties of the wave function
To find the wave function, Schrodinger’s equation must be solved.
But since it is a second order differential equation, there is not one but several solutions.
We must select those wave functions which would correspond meaningfully to a physical
system.
Such wave functions are said to be acceptable wave functions. To be an acceptable wave
function, it must possess the following properties.
Property 1:  is single valued everywhere.
A function f(x) which is not a single valued over a certain interval is shown.

Here f(x) has three values f1, f2 & f3 for the same value of P at x = P.
As f1  f2  f3 it means to say that, if f(x) were to be the wave function, then the probability of
finding the particle has three different values at the same location which is absurd.
Hence the wave function is not acceptable.

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Property 2:  is finite everywhere.

A function f(x) which is not finite at x = Q is as shown

At x = Q, f(x) = .
Thus, if f(x) were to be a wave function, it signifies a large probability of finding the particle
at a single location (x = Q), which violates the uncertainty principle.
Hence wave function becomes unacceptable.

Property 3:  & its first derivatives w.r.t. its variable is continuous everywhere.

Function f(x) which is discontinuous at R is as shown.

At x = R, f(x) is truncated at A & restarts at B.
If f(x) were to be wave function, then the state of the system at x = R cannot be ascertained.
Hence the wave function is not acceptable.
Also, when  is not continuous, its first derivatives will not be finite.
As a requirement apart from being finite, their first derivatives should also be continuous, if
they are not continuous, the second derivatives of  will not be finite.
But we need second derivatives in evaluating the Schrodinger’s equation.
Property 4:
For bound state,  must vanish at infinity.
If  is a complex function, then * must vanish at infinity.
* is the complex conjugate of 

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Eigen functions & eigen values
Eigen functions are those wave functions of quantum mechanics which possess the properties
that they are single valued & finite everywhere, also their first derivative with respect to their
variables are continuous everywhere.
Operator operating on eigen function produces back the wave function multiplied by a constant.
Such values obtained for physical observables are called eigen values.

Example: 𝐴̂=
where  is the operator for the physical quantity &  is the eigen function.
Such values () obtained for a physical observable are called eigen values.
Time independent Schrodinger’s wave equation
Based on the de broglie’s idea of matter waves, Schrodinger developed a mathematical theory
which plays the same role as Newton’s law in classical mechanics.
According to the de Broglie theory, for a particle of mass m, moving with a velocity v,
associated with it is a wavelength,
ℎ
𝜆 = 𝑝 …………. (1)

Here, p is the momentum of the particle.

The wave equation for a de Broglie wave considered traveling in positive x-direction can be in
the complex notation as
Ψ = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) …………. (2)
 is the total wave function, A is a constant & is the angular frequency.
The time independent part in equation (2) can be represented as the wave function 𝜓 = 𝐴𝑒 𝑖𝑘𝑥
Therefore, equation (2) becomes.
Ψ = 𝜓𝑒 −𝑖𝜔𝑡 ……..…… (3)
Differentiating  twice w.r.t. x, we have
𝑑2 Ψ 𝑑2 𝜓
= 𝑒 −𝑖𝜔𝑡 …….. (4)
𝑑𝑥 2 𝑑𝑥 2

Now differentiating  twice w.r.t. t, we get

𝑑2 Ψ
= −𝜔2 𝑒 −𝑖𝜔𝑡 𝜓 ……. (5)
𝑑𝑡 2

𝒅𝟐 𝐲 𝟏 𝒅𝟐 𝐲
We have the equation for a traveling wave as 𝒅𝒙𝟐 = 𝒗𝟐 𝒅𝒕𝟐

where y is the displacement and v the velocity of the wave.

The wave equation for the de Broglie wave for the motion of a free particle can be represented
as

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𝑑2 Ψ 1 𝑑2 Ψ
= 𝑣2 ……. (6)
𝑑𝑥 2 𝑑𝑡 2

The above equation represents the wave propagating along x-axis with a velocity v & is
displacement at the time t.
 Using equations (4) & (5), equation (6) becomes
𝑑2𝜓 1
𝑒 −𝑖𝜔𝑡 2
= 2 (−𝜔2 𝑒 −𝑖𝜔𝑡 𝜓)
𝑑𝑥 𝑣
𝑑2 𝜓 𝜔2 𝜓
Simplifying further, =−
𝑑𝑥 2 𝑣2

If  &  are the wavelength & frequency of the wave, then  = 2 & v = 
Substituting for  & v, the above equation becomes
𝑑2 𝜓 4𝜋 2 𝜓
=−
𝑑𝑥 2 2

1 1 𝑑2 𝜓
2 =− …………………. (7)
 4𝜋 2 𝜓 𝑑𝑥 2

For a particle of mass m moving with a velocity v,

1 𝑚2 𝑣 2 𝑝2
Kinetic energy is 2 𝑚𝑣 2 = = 2𝑚 …………… (8)
2𝑚
ℎ
But from equation (1), 𝑝 =


ℎ2 1
Substituting for ‘p’ in (8), Kinetic energy is = 2𝑚 ………. (9)
2

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Substituting for 2 from equation (7), now equation (9) can be rewritten as

ℎ2 1 𝑑2 𝜓 ℎ2 𝑑2 𝜓
Kinetic energy = 2𝑚 (− )=− …………. (10)
4𝜋2 𝜓 𝑑𝑥 2 8𝜋 2 𝑚𝜓 𝑑𝑥 2

Let there be a field where the particle is present. Depending on its position in the field, the
particle will possess certain potential energy V, then the total energy E of the particle is the
sum of kinetic energy and potential energy.
Using equation (10), the total energy E can be written as
ℎ2 𝑑2 𝜓
𝐸=− + 𝑉 ………. (11)
8𝜋 2 𝑚𝜓 𝑑𝑥 2

ℎ2 1 𝑑2 𝜓
Re-arranging equation (11), we get 𝐸 − 𝑉 = − 8𝜋2 𝑚 𝜓 𝑑𝑥 2

8𝜋 2 𝑚 𝜓 𝑑2𝜓
(𝐸 − 𝑉) = −
ℎ2 𝑑𝑥 2
𝑑2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0…………. (12)
𝑑𝑥 2 ℎ2

This is the time independent Schrodinger’s wave equation.

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Eigen values & eigen functions for a particle in one-dimensional well of infinite height

Consider a particle of mass m free to move in x-direction in the region from x=0 to x= a.
Outside this region, the potential energy V is taken be infinite & within this region it is zero
(which means that the particle is bound within the limits x = 0 to x = a)
Time independent Schrodinger’s wave equation is:
𝑑2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓 = 0
𝑑𝑥 2 ℎ2

Outside the well (V=∞)

Schrodinger’s equation becomes
𝑑2 𝜓 8𝜋 2 𝑚
+ (𝐸 − ∞)𝜓 = 0 ………… (1)
𝑑𝑥 2 ℎ2

This equation holds good only if 𝜓 = 0 for all points outside the well.
Therefore |𝜓|2 = 0, which means that the probability density is zero.
Hence, the particle cannot be found at all outside the well ……… (Condition-I)
Inside the well (V=𝟎),
Schrodinger’s equation is:
𝑑2 𝜓 8𝜋 2 𝑚
+ (𝐸 − 0)𝜓 = 0
𝑑𝑥 2 ℎ2
𝑑2𝜓 8𝜋2 𝑚
+ 𝐸 𝜓 = 0 ………… (2)
𝑑𝑥 2 ℎ2
8𝜋 2 𝑚
In equation (2), let 𝐸 = 𝐾 2 ………… (3)
ℎ2

Hence, equation (2) becomes:

𝑑2 𝜓
+ 𝐾 2 𝜓 = 0 ………………. (4)
𝑑𝑥 2

The solution of the above equation is given as

𝜓 = C cosKx + D SinKx ……………. (5)

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As per condition I, 𝜓 = 0. Hence, equation (5) becomes
0 = C cos0 + D Sin0
0= C ×1+D×0
Hence, C = 0 ………… (6)
Also, from condition I, at x=a,𝜓 = 0 . Therefore, equation (5) becomes
0 = C cosKa + D SinKa
But from equation (6), C=0, hence the above equation will be
D SinKa = 0
Here D need not be zero (if D=0, then 𝜓 = 0 in equation (5), and hence |𝜓|2 = 0 which means
particle is not present inside the well which is not true)
Therefore, SinKa = 0 or Ka = n𝜋, where n=0,1,2,3……
n𝜋
Hence, K = ……………. (7)
𝑎

Substituting for C & K from equations (6) & (7), equation (5) can be written as
n𝜋
𝜓𝑛 = D Sin x ……………. (8)
𝑎

which represents the permitted solutions.

To evaluate D in equation (8), one must perform the normalization of the wave function.
Since there is only one particle & at any time it is present somewhere inside the well only,
hence integral of the wave function over the entire space in the well must be equal to unity.
𝑎
Hence ∫0 |𝜓𝑛 |2 𝑑𝑥 = 1 ……………. (9)

Substituting for 𝜓𝑛 from equation (8) in (9), we get

𝑎 n𝜋
∫0 𝐷2 Sin2 ( 𝑎 )x dx = 1
1−𝑐𝑜𝑠2𝜃
From trigonometry, W.K.T. 𝑠𝑖𝑛2 𝜃 = ( )
2

Therefore, the normalization equation becomes:

1 𝑎 1 𝑎 2𝑛𝜋
𝐷2 [ 2 ∫0 𝑑𝑥 − 2 ∫0 𝑐𝑜𝑠 𝑥 𝑑𝑥] = 1
𝑎
𝑎 𝑎
𝐷2 2𝑛𝜋
[ ∫ 𝑑𝑥 − ∫ 𝑐𝑜𝑠 𝑥 𝑑𝑥] = 1
2 0 0 𝑎

𝐷2 𝑎 2𝑛𝜋 𝑎
[𝑥 − 𝑠𝑖𝑛 𝑥] = 1
2 2𝑛𝜋 𝑎 0

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𝐷2 𝑎 2𝑛𝜋
[𝑎 − {𝑠𝑖𝑛 𝑎 − sin 0} ] = 1
2 2𝑛𝜋 𝑎
𝐷2 𝑎
[𝑎 − 2𝑛𝜋 {𝑠𝑖𝑛2𝑛𝜋 − 0} ] = 1
2

𝐷2
[𝑎 − 0] = 1
2

𝐷2 𝑎
=1
2

2 2
𝐷2 = 𝑎 or 𝐷 = √𝑎

Thus, the normalized wave function of a particle in a one-dimensional potential well of infinite
height is

2 𝑛𝜋
𝜓𝑛 = √ 𝑎 𝑠𝑖𝑛 ( 𝑎 ) 𝑥 …………………… (10)

Substituting the value of k from (7) In (4), we have

8 𝜋2𝑚 𝑛𝜋 2 𝑛2 ℎ 2
E=(𝑎) or 𝐸 = 8𝑚𝑎2
ℎ2

This is the energy eigen value for a particle in one dimensional potential well of infinite height.

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