AK 1

WAVE MECHANICS
The quantity that characterizes the de Broglie waves is called the wave function.

 Ψ = 𝐴𝑒 ( )

 wave function is an essential element of a quantum mechanical system .

 any meaningful information about a quantum mechanical system can be obtained
from wave function.
 It is denoted by Ψ(𝑟,⃗ t) for 3-dimensional motion of a system.

Physical significance of ψ:

 The probability that a particle will be found at a given place in space at a given
instant of time is characterized by the function ψ (x, y, z, t). It is called the wave
function.
 This function can be either real or complex. The only quantity having a physical
meaning is the square of its magnitude P = |ψ| = ψψ* where ψ* is the complex
conjugate of ψ.
 The quantity P is the probability density. The probability of finding a particle in
a volume dx, dy, dz is |ψ| dx dy dz. Further, since the particle is certainly to be
found somewhere in space

∫∫∫ |ψ| dx dy dz = 1

the triple integral extending over all possible values of x, y, z. A wave function (ψ)
satisfying this relation is called a normalized wave function.

Orthogonal and normalized wave functions.

 If the product of a function ψ (x) and the complex conjugate ψ * (x) of a

function ψ (x) vanishes when integrated with respect to x over the interval a ≤ x
≤ b, that is, if
∗
∫ ψ (x) ψ (x) dx = 0

then ψ (x) and ψ (x) are said to be orthogonal in the interval (a, b)
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We know that the probability of finding a particle in the volume element dV is

given by ψψ∗ dV. The total probability of finding the particle in the entire space is, of
course, unity, i.e., |ψ| dV = 1.

where the integration extends over all space. The above equation can also be written as
ψψ∗ dV = 1.

Any wave function satisfying the above equation is said to be normalized to unity
or simply normalized. Very often ψ is not a normalized wave function. We know that it
is possible to multiply ψ by a constant A, to give a new wave function, Aψ, which is
also a solution of the wave equation.

∫(Aψ) ∗ Aψ dx dy dz = 1

Or

∫ |A| ψψ*dx dy dz = 1

Or
1
|A| =
∫ ψψ ∗ dx dy dz

|A| is known as normalizing constant.

Time dependent Schrodinger’s equation

The quantity that characterizes the de Broglie waves is called the wave function. It is
denoted by ψ. It may be a complex function. Let us assume that ψ is specified in the x
direction by
( )
Ψ = 𝐴𝑒 .…... (1)

Where k is wave vector 𝑘 = , 𝜔 is angular frequency 𝜔 = 2𝜋𝜗

Let E be the total energy and P the momentum of the particle. Then E = h𝜗 and

λ = h/p

 If 𝜗 is the frequency, then 𝐸 = ℎ𝜗 , multiply and divided by 2𝜋 then

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𝐸= 2𝜋𝜗 where 𝜔 = 2𝜋𝜗 is the angular frequency

Then 𝐸 = 𝜔, ℏ=

𝜔 = ……(2)
ℏ

𝑃= multiply and divided by 2𝜋 then

𝑃= = = 𝑘 where wave vector 𝑘 =

𝑘 = ……..(3)
ℏ

Substitute values of (2) and (3) in (1)

( )
Ψ = 𝐴𝑒 ℏ ……(4)

Eq. (4) is a mathematical description of the wave equivalent of an unrestricted particle

of total energy E and momentum P moving in the +x direction.

Differentiating Eq. (4) twice with respect to x, we get

𝝏𝟐 𝚿 𝑷𝟐
=− 𝚿…..(5)
𝝏𝒙𝟐 ℏ𝟐

Differentiating Eq. (4) once with respect to t, we get

𝝏𝚿 𝒊𝑬
= − 𝚿 … … (𝟔)
𝝏𝒕 ℏ

At speeds small compared with that of light, the total energy E of a particle is the sum
of its kinetic energy and its potential energy V. V is in general a function of
position x and time t.

𝐏𝟐
𝐄= + 𝐕……..(7)
𝟐𝐦
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Multiplying both sides of Eq. (7) by ψ we get

𝐸𝜓 = 𝜓 + 𝑉𝜓…….(8)

From Eqs. (6) and (5) we see that

ℏ Ψ Ψ
𝐸𝜓=− ……..(9) And 𝑃 𝜓 = −ℏ𝟐 ………(10)

Substituting these expressions for Eψ and 𝑃 ψ into Eq. (8) we obtain

ℏ Ψ ℏ𝟐 Ψ
− =− + 𝑉𝜓

Or
Ψ ℏ𝟐 Ψ
iℏ =− + 𝑉𝜓……….(11)

Eq. (11) is the time-dependent form of Schrodinger’s equation.

In three dimensions the time-dependent form of Schrodinger’s equation is

ℏ𝟐
iℏ
Ψ
=− ( Ψ
+
Ψ
+
Ψ
)+V𝜓
ℏ𝟐
∇ =( )
Ψ Ψ Ψ Ψ
iℏ =− ∇ 𝜓 + V𝜓 + +

Ψ
=− ( Ψ
+
Ψ
+
Ψ
)+V𝜓
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Time Independent Schrodinger’s equation

In a great many situations, the potential energy of a particle does not depend upon
time explicitly. The forces that act upon it, and hence V, vary with the position of the
particle only. When this is true, Schrodinger’s equation may be simplified by removing
all reference to t. The one-dimensional wave function ψ of an unrestricted particle may
be written in the form

( )
Ψ = 𝐴𝑒 ℏ

( )
Ψ = 𝐴[𝑒 ℏ .𝑒 ℏ ] where Ψ° = 𝐴𝑒 ℏ

( )
Ψ = Ψ° . 𝐴𝑒 ℏ ……(1)

Here,. Ψ° = 𝐴𝑒 ℏ That is, ψ is the product of a position dependent function ψ0 and a

( )
time dependent function 𝐴𝑒 ℏ ℏ=

Differentiating Eq. (1) with respect to t, we get

Ψ ( )
=− Ψ° . 𝑒 ℏ ………(2)
ℏ

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

Ψ ° ( )
= .𝑒 ℏ ………..(3)

We can substitute Eq.(2) and (3) values in the time-dependent form of Schrodinger’s
equation
Ψ ℏ Ψ
𝑖ℏ =− +V𝜓 …..Time dependent Schrodinger equation

( ) ℏ Ψ° ( ) ( )
𝐸Ψ° 𝑒 ℏ =− 𝑒 ℏ + VΨ° 𝑒 ℏ

( )
Dividing the above equation by common exponential factor ie 𝑒 ℏ , we get

ℏ Ψ°
𝐸Ψ° = − + VΨ°
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Ψ°
+ (𝐸 − 𝑉 )Ψ° = 0……(4)
ℏ

In three dimensions it is
𝟐𝒎
𝛁 𝟐 𝚿° + (𝑬 − 𝑽)𝚿° = 𝟎………(5)
ℏ𝟐

Eq. (5) is the steady-state or time independent form of Schrodinger’s equation.

Usually, it is written in the form

𝟐𝒎
𝛁𝟐 𝚿 + (𝑬 − 𝑽)𝚿 = 𝟎
ℏ𝟐

Eigenfunctions and Eigenvalues.

 Schrodinger’s time-independent equation is an example of a type of differential

equation called an eigenvalue equation.
 In general, we can write an eigenvalue equation as 𝐹 ψ = fψ The differential
operator 𝐹 operates on a function ψ, and this yields a constant f times the
function.
 The function ψ is then called an eigenfunction of the operator 𝐹 ,and the
corresponding value for f is called the eigenvalue.
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Particle in a Box
 Consider a particle moving inside a box along the x-direction. The particle is
bouncing back and forth between the walls of the box.
 The box has insuperable potential barriers at x=0 and x=L, i.e., the box is
supposed to have walls of infinite height at x=0 and x=L.
 The particle has a mass m and its position x at any instant is given by 0<x<L.

The potential energy V of the particle is infinite on both sides of the box. The
potential energy V of the particle can be assumed to be zero between x=0 and x=L.

In terms of the boundary conditions imposed by the problem, the potential

function is

𝑉 = 0 𝑓𝑜𝑟 0 < 𝑥 < 𝐿

𝑉 = ∞ 𝑓𝑜𝑟 𝑥 ≤ 0

𝑉 = ∞ 𝑓𝑜𝑟 𝑥 ≥ 𝐿

The particle cannot exist outside the box and so its wave
function Ψ is for 𝑥 ≤ 0 and 𝑥 ≥ 𝐿. We have to find what
Ψ is within the box, between x=0 and x=L.

Within the box, the Schrodinger’s equation becomes

𝑑 Ψ 2𝑚 2𝑚𝐸
+ 𝐸Ψ = 0 =𝐾
𝑑𝑥 ℏ ℏ

Putting 𝐾 in the above equation

𝑑 Ψ
+𝐾 Ψ=0
𝑑𝑥
The general solution of this equation is

Ψ = A sin kx + B cos kx … … … (1)

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The boundary conditions can be used to evaluate the constants A and B in equation (1).

Ψ = 0 at x = 0 and hence B = 0

Ψ = 0 at x = L hence 0 = A sin 𝑘𝐿

Since 𝐴 ≠ 0, 𝐾𝐿 = 𝑛𝜋 where n is a integer or 𝑘 =

𝑛 𝜋
𝑘 =
𝐿

Thus Ψ (𝑥) = 𝐴 sin … … … . (2)

The energy of the particle is,

Comparing both the 𝑘 values

𝑛 𝜋 2𝑚𝐸
= … … … (∗)
𝐿 ℏ

ℏ= ℏ =

substituting the value of ℏ then equation (*) becomes

𝑛 𝜋 2𝑚𝐸
=
𝐿 ℎ
( )
4𝜋

Solving for energy 𝐸 =

𝑛 ℎ
∴ 𝐸 = … … … . (3)
8𝑚𝐿
For each value of n, there is an energy level and the corresponding wavefunction
is given by equation (2). Each value of 𝐸 is called an eigenvalue and the corresponding
Ψ is called eigenfunction. Thus, inside the box, the particle can only have the discrete
energy values specified by equation (3). Note also that the particle cannot have zero
energy.
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Linear harmonic oscillator

Consider a particle executing simple harmonic motion along the x direction and
let k be the restoring force unit displacement.

The P.E. of the particle = ∫ 𝑘𝑥𝑑𝑥 = 𝑘𝑥

The Schrodinger equation for the harmonic oscillator is

𝑑 Ψ 8𝜋 𝑚 1
+ 𝐸 − 𝑘𝑥 Ψ = 0 … … … (1)
𝑑𝑥 ℎ 2
It is convenient to simplify Eq. (1) by introducing the dimensionless quantities

1 2𝜋𝑚𝑣
𝑦= √𝑘𝑚 𝑥= 𝑥 … … … … … (2)
ℎ ℎ
2𝜋 2𝜋

2𝐸 𝑚 2𝐸
𝛼= = … … … . . (3)
ℎ 𝑘 ℎ𝑣
2𝜋

Where v is the classical frequency of the oscillation given by

1 𝑘
𝑣=
2𝜋 𝑚

In terms of y and 𝛼, Schrodinger’s equation becomes

𝑑 Ψ
+ (𝛼 − 𝑦 )Ψ = 0 … … … … . . (4)
𝑑𝑥
To solve this equation, a solution of the form below can be tried:

Ψ = 𝑓(y)𝑒 … … … … … . . (5)

Where 𝑓(y) is a function of y that remains to be found.

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By inserting theΨof Eq. (5) in Eq. (4) we obtain

𝑑 𝑓 𝑑𝑓
− 2𝑦 + (𝛼 − 1)𝑓 = 0 … … … … … . (6)
𝑑𝑦 dy

Which is the differential equation that 𝑓 obeys.

Writing (𝛼 − 1) = 2𝑛, Eq. (6) becomes,

𝑑 𝑓 𝑑𝑓
− 2𝑦 + 2𝑛𝑓 = 0 … … … … … … . (7)
𝑑𝑦 dy

This is a standard mathematical equation known as Hermite’s equation.

The solution of Eq. (7) is called Hermite’s Polynomials, given by

𝑑
H (𝑦) = 𝑓(y) = (−1) exp 𝑦 [exp (−𝑦 )] … … … … … (8)
𝑑𝑦

The eigen functions of harmonic oscillator, therefore, are the following:

−𝑦
Ψ (𝑦) = 𝑁H (𝑦) exp … … … … (9)
2

Where N is a normalization constant.

The eigen values (permitted values of the total energy) are given by,
1
𝐸 = 𝑛+ ℎ𝑣, 𝑛 = 0,1,2,3. … … … … … . . (10)
2
The energy of a harmonic oscillator is thus
quantized in steps of hv. The energy levels here are
evenly spaced. We note that, when n=0, 𝑬𝟎 =
𝟏
𝒉𝒗 which is the lowest value of energy the
𝟐
oscillator can have. This value is called zero-point
energy.
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