Schrödinger Equation

3. The Schrödinger Equation

Facts about wave function ()

 A wave function is a mathematical function, such as sin , which

may be large in one region, small in others and zero elsewhere.
  gives all the information needed to know about the location
and the motion of the particle it describes.

 If at a particular point  is large, the particle has high probability

of being at that point. If  is zero, the particle will not be found
there.
 If  changes rapidly from place to place, it indicates that the
kinetic energy of the particle is high.
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 Schrödinger Equation

3.1. Derivation of Schrödinger's Equation

 For a wave traveling in the +x direction, the one-dimensional
wave equation is:
𝑥
−𝑖𝜔 𝑡−
𝑦 = 𝐴𝑒
A = maximum displacement in the y direction
 = angular frequency
 = velocity

y is a complex quantity that contains real and imaginary parts.

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 Schrödinger Equation

 In quantum mechanics, y is substituted by the wave function,

𝑥
−𝑖𝜔 𝑡−
 = 𝐴𝑒

Let  = 2, where  is linear frequency and  = 

  Ae2 i ( t  x /  )
and considering the wave property of a particle
 E/h
Hence,

 h/ P
2i
 ( E t  P x)
  Ae h
(1)
The Equation holds for freely moving particles without restricting
conditions. 3
 Schrödinger Equation

3.1.1. The Time-dependent SchrÖdinger Equation

Differentiate equation (1) twice with respect to x.

d2 4 2 P 2
2
 2

dx h
Note that i2 = -1. Rearrangement yields,
h2 d 2 (2)
P   2 2
2

4 dx
Differentiating Equation (1) once with respect to t
d 2 i E
  
dt h
h d
   E (3)
2 i dt
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 Schrödinger Equation

1 1 𝑚 22 𝑃 2
𝐸 = 𝑇 + 𝑉 = 𝑚2 + 𝑉 = +𝑉 = +𝑉
2 2 𝑚 2𝑚

𝑃2
Multiply the equation by  gives  + 𝑉 = 𝐸 (4)
2𝑚

Substitute Eq (2) and (3) in (4).

h2 d2 ih d
 2   V   (5)
8 m dx 2
2 dt
h2 ih d
In three dimensions:  2  2 ( x , y , z )  V ( x , y , z )   ( x, y, z )
8 m 2 dt

time-dependent Schrödinger Equation

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 Schrödinger Equation

3.1.2. The Time-independent Schrödinger Equation

2 i 2 iPx  2 iEt
 (Et  P x)
  Ae h
 Ae h
.e
h
Equation (1) may be written in a form composed of position-
dependent (x) and time-dependent terms (t):
2i
 Et
  ( x ) e h

Insert this equation into the time dependent Schrödinger equation

gives
2 i 2 i 2 i
h2 d 2  Et  Et  Et
 2  e h
 V ( x ) e h
 E ( x ) e h
8 m dx 2 ( x)

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 Schrödinger Equation

2i
 Et
Divide the above equation by e h
Rearrangement yields,
d2 8 2 m
 ( x )  2 ( E  V ) ( x )  0
dx 2
h (6)
time-independent Schrödinger Equation
In three dimensions,


Another form: H  ( x )  E ( x )

h2 d2
Where H 
8 2 m dx 2
 V
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 Schrödinger Equation

3.2 Interpretation of a wave function and requirements for an

acceptable wave function

Interpretation of a wave function

1. Probability Interpretation - Born Postulate

The probability of finding a particle at a position x is given by |(x,t)|2.

Probability(at x) = |(x,t)|2
The probability of finding a particle at time t between x and x + dx is
|(r,t)|2 = *dx.
i.e.,
Probabilty(between x and x + dx) = |(x,t)|2 = *dx
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 Schrödinger Equation

2. Normalization
The probability of finding a particle somewhere in the universe is
unity.


 ( x,t ) dx 1
 2


In three dimensions,


 d  1
 2


where d = dxdydz
If  is a complex function,


 d 1
 *



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 Schrödinger Equation

3. Orthogonality
 Each particle must be described by a wave function different
from all other particles in a system.


 

1 2 d  0

4. Linear combination of wave functions

 Any linear combination of two or more solutions is also a
solution of the Schrödinger equation.
n
   ai i
i

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 Schrödinger Equation

5. Average Values
 The average value of the physical quantity associated with an
operator in a system described by  can be calculated using the
equation:

 B   B d
*

Where

B is the quantum mechanical operator associated with the physical
quantity B, and  B is the average value of B.

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 Schrödinger Equation

Requirements
It is required that  be
1. Finite
2. Continuous
3. Single valued
4. Have a continuous slope

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4. Operators in Quantum Mechanics
4.1 Introduction
An operator is a rule for transforming a given function into
another function.
For example:
𝑑
The operator transforms a function into its first derivative:
𝑑𝑥

d
f ( x)  f ' ( x)
dx

If A transforms the function f(x) into the function

g(x), we write: A f ( x)  g ( x)
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 Quantum Mechanical Operators

Sum of operators:     

 A  B  f ( x)  A f ( x)  B f ( x)
 

 d  d
For example:  ln   f ( x )  ln f ( x )  f ( x )  ln f ( x )  f '
( x)
 dx  dx

 
 
Square of operators: A f ( x)  A  A f ( x ) 
2

 

 d   d    d2 
2
d 
For example:   f ( x)      f ( x)    2  f ( x)
 dx   dx   dx    dx 
2
d  d2
Therefore    2
 dx  dx
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 Quantum Mechanical Operators

Product of operators

  

 A B  f ( x)  A  B  f ( x)
   
Example

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 Quantum Mechanical Operators

Solution

a)

b)

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 Quantum Mechanical Operators
 
 
c) In this example A B and B A produce different results when
they operate on f(x).
So, they are not equal.

Linear Operator:
The operator satisfies the following two conditions.

Commutator: The commutator of two operators is

defined as
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 Quantum Mechanical Operators

 To operators are said to commute if

Postulate
 To every observable in classical mechanics there corresponds a
linear operator in quantum mechanics.
 In quantum mechanics each physical property of a system has a
corresponding operator.

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 Quantum Mechanical Operators

Eg.

1. Observable: Position (x) multiply by x


Operator: x

2. Observable: Momentum (Px)

  

Operator: Px , Py , Pz

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 Quantum Mechanical Operators

3. Observable: Potential Energy (Vx)


Operator: V (x ) Multiply by V (x)

4. Observable: Kinetic energy (T)


Operator: T

 ℎ2 𝜕2
T= − 2
4𝜋 𝑚 𝜕𝑥2

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 Quantum Mechanical Operators

5. Observable: Total energy (E)

Operator: The Hamiltonian Operator ( )

Defining the Laplacian operator,∇2 by

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 Quantum Mechanical Operators

4.2. Eignfunction and Eignvalue

 When an operator applied to the function f gives the
function back again but multiplied by a constant c, that is,
when

One says that f is an eignfunction of with eignvalue of c.

 The wave functions and operators generally are complex

quantities, but certainly the eignvalues must be real
quantities if they are to correspond to the results of
experimental measurements.
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 Quantum Mechanical Operators

 The eignvalues of an operator, , will be real if it satisfies

the equation:

Hermitian operator:
 An operator that satisfies the above equation
Example
Prove that the kinetic energy operator is Hermitian.
Solution

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 Quantum Mechanical Operators

Hence, the kinetic energy operator is Hermitian.

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 Quantum Mechanical Operators

4.3. Important Theorems of Hermitian operators

 The eigenvalues of the operator corresponding to the
physical quantity a are the possible results of a
measurement of a,
Therefore,
 The eigenvalues should all be real numbers.
Theorem 1
 The eigenvalues of a Hermitian operator are real numbers.
Theorem 2
 Two eigenfunctions of a Hermitian operator that
correspond to different eigenvalues are orthogonal.
 Eigenfunctions of that belong to a degenerate eigenvalue
can always be chosen to be orthogonal.
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4.4. Angular Momentum

 It is a fundamental property of rotating systems

Linear momentum (P) = m
 Consider a particle rotating in a plane about a fixed center

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 Angular momentum

Let rot be frequency of rotation (cycles/second)

The velocity of the particle,
 = 2r rot
Angular velocity,
rot = 2 rot (radian/s)
Then,
 = rrot
Therefore,

Where 𝐼 = 𝑚𝑟2 is the momentum of inertia

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 Angular momentum

Compare the first and the last expressions.

I m   

Angular momentum (l)

For a rotating system,

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