Nanophysics

Lecture-2

Dr. Kazi Hanium Maria

Course Code: PHY 171
Course teacher

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 4. Wave Mechanics
• Recall – the wavefunction () contains all the information we need to
know about any particular system.
• How do we determine  and use it to deduce properties of the
system?

4.1 Operators and Observables

• If  is the wavefunction representing a system, we can write:

෠ = 𝑄Ψ
𝑄Ψ

where 𝑄– “observable” property of system (e.g. energy,

momentum, dipole moment …)
𝑄෠ – operator corresponding to observable 𝑄.
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• This is an eigenvalue equation and can be rewritten as:

෠ = 𝑄Ψ
𝑄Ψ
operator 𝑄෠ acting on function  multiplied
function  by a number 𝑄
(eigenfunction) (eigenvalue)

(Note:  can’t be cancelled).

Examples: d/dx (eax) = a eax

d2/dx2 (sin ax) = −a2 sin ax

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An operator is a mathematical object acting on the system’s state
vector and producing another. Consider 𝐴መ is an operator and |ψ⟩ is an
element of the Hilbert space of the system, then 𝐴መ |𝜓⟩ = |𝜙⟩, where |𝜙⟩
is the another state vector also belongs to the same Hilbert space.

“Operators in quantum mechanics are mathematical entities used to

represent physical processes that result in the change of the state
vector of the system, such as the evolution of these states with time.
These operators can also represent physical properties of a system
that can be experimentally measured (for example position,
momentum, or energy), the observables associated to this quantum
system.”

A Hilbert space is an inner product space that is complete with respect

to the norm defined by the inner product. ℋ = {Ψ(𝑥𝑖 )}

4
Linear operators: An operator is said to be a liner if it operates on the
sum of two or more functions and gives the result as the sum of the
operation results on each function.

If 𝐴መ is applied on the sum of two functions Ψ(𝑥) and Φ(𝑥), the linear
operator gives:
𝐴መ Ψ 𝑥 + Φ 𝑥 = 𝐴Ψ መ 𝑥 + 𝐴Φመ 𝑥

መ
𝐴𝑐Ψ መ 𝑥
𝑥 = 𝑐 𝐴Ψ

1. Squaring a function is not linear. Let, Ψ 𝑥 = 𝑥 2 and Φ 𝑥 = 𝑥:

𝐴መ 𝑎𝑥 2 + 𝑏𝑥 = (𝑎𝑥 2 + 𝑏𝑥)2 = 𝑎2 𝑥 4 + 2𝑎𝑏𝑥 4 + 𝑏 2 𝑥 2
መ 2 + 𝑏𝐴𝑥
𝑎𝐴𝑥 መ = 𝑎𝑥 4 + 𝑏𝑥 2
So, 𝐴መ 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 ≠ 𝑎𝐴Ψ መ 𝑥 + 𝑏𝐴Φ(𝑥)
መ and 𝐴መ is not linear

2. Differentiation is linear:
𝜕 𝜕Ψ(𝑥) 𝜕Φ(𝑥)
𝐴መ 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 = 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 =𝑎 +𝑏 መ 𝑥 + 𝑏𝐴Φ(𝑥)
= 𝑎𝐴Ψ መ
𝜕𝑥 𝜕𝑥 𝜕𝑥

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3. Integrating from 0 to 𝑥 is linear:
𝑥
𝐴መ 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 = ‫׬‬0 (𝑎Ψ 𝑥 ′ + 𝑏Φ 𝑥 ′ )𝑑𝑥 ′
𝑥 𝑥
መ 𝑥 + 𝑏𝐴Φ(𝑥)
= 𝑎 ‫׬‬0 Ψ 𝑥 ′ 𝑑𝑥 ′ + 𝑏 ‫׬‬0 Φ 𝑥 ′ 𝑑𝑥 ′ = 𝑎𝐴Ψ መ

4. Adding is not linear. Let, Ψ 𝑥 = 𝑥 2 and Φ 𝑥 = 𝑥: Let, 𝐴መ is adding 3.

𝐴መ 𝑎𝑥 2 + 𝑏𝑥 = 𝑎𝑥 2 + 𝑏𝑥 + 3
መ 2 + 𝑏𝐴𝑥
𝑎𝐴𝑥 መ = 𝑎𝑥 2 + 3 + 𝑏𝑥 + 3 = 𝑎𝑥 2 + 𝑏𝑥 + 6
So, 𝐴መ 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 ≠ 𝑎𝐴Ψ መ 𝑥 + 𝑏𝐴Φ(𝑥)
መ and 𝐴መ is not linear

5. Mapping to a fixed function is not linear. Let, Ψ 𝑥 = 𝑥 2 and Φ 𝑥 = 𝑥:

𝐴መ ℎ 𝑎𝑥 2 + 𝑏𝑥 = ℎ(𝑥)
𝑎𝐴መ ℎ 𝑥 2 + 𝑏𝐴መ ℎ 𝑥 = 𝑎ℎ(𝑥) + 𝑏ℎ(𝑥)
So, 𝐴መ ℎ 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 ≠ 𝑎𝐴መ ℎ Ψ 𝑥 + 𝑏𝐴መ ℎ Φ(𝑥) and 𝐴መ ℎ is not linear.

6. Translating Ψ 𝑥 by 𝐿 is linear.
𝐴መ 𝐿 𝑎Ψ 𝑥 + 𝑏Φ 𝑥 = 𝑎Ψ 𝑥 − 𝐿 + 𝑏Φ 𝑥 − 𝐿 = 𝑎𝐴መ 𝐿 Ψ 𝑥 + 𝑏𝐴መ 𝐿 Φ(𝑥)

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Eigen operators: An operator is said to be an Eigen operator if it operates
on a function and giving a function which is the original function
multiplied by some constant.
መ 𝑥 = 𝛼Ψ(𝑥)
𝐴Ψ

Ex: 𝐻Ψ = 𝐸Ψ
𝜕 𝜕2 𝜕𝑛
Ex: 𝑒 𝑎𝑥 is a eigen function of , ,
𝜕 𝜕 2 𝜕 𝑛
𝜕𝑛
𝑒 𝑎𝑥 = 𝑎𝑛 𝑒 𝑎𝑥 , 𝑎𝑛 is eigen value
𝜕𝑛

Addition of operators: 𝐴መ + 𝐵෠ Ψ 𝑥 = 𝐴Ψ
መ 𝑥 + 𝐵Ψ(𝑥)
෠

Subtraction of operators: 𝐴መ − 𝐵෠ Ψ 𝑥 = 𝐴Ψ
መ 𝑥 − 𝐵Ψ(𝑥)
෠

Multiplication of operators: 𝐴መ 𝐵෠ Ψ 𝑥 = 𝐴Ψ𝐼

መ 𝑥 = Ψ " (𝑥)
2
መ
Ex: 𝐴2 Ψ 𝑥 ≠ 𝐴Ψ(𝑥) , let, Ψ 𝑥 = 5𝑥 2 + 3𝑥
𝜕2 2
𝜕 𝜕 2
𝜕
5𝑥 + 3𝑥 = 5𝑥 + 3𝑥 = 10𝑥 + 3 = 10
𝜕2 𝜕 𝜕 𝜕
𝜕
መ
[𝐴Ψ(𝑥)] = { (5𝑥 2 + 3𝑥)}2 = 100𝑥 2 + 60𝑥 + 9
2 7
𝜕
 The constant ‘𝛼’ is called Eigen value and function Ψ(𝑥) is
called Eigen function or characteristic function or proper
መ
function of the operator 𝐴.

𝑑2
For example, when an operator is carried out on function
𝑑𝑥 2

cos 2𝑥.

𝑑2
− 2 (cos 2𝑥) = 4(𝑐𝑜𝑠2𝑥)
𝑑𝑥
In this case, 𝑐𝑜𝑠2𝑥 is the eigen function and 4 is Eigen value
𝑑2
of the operator -
𝑑𝑥 2

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Hermitian operator: An operator is called Hermitian when it can
always be flipped over to the other side if it appears in an inner
product:
መ = 𝐴𝑓
𝑓 𝐴𝑔 መ 𝑔 always if 𝐴መ is Hermitian.

Operators that are their own Hermitian Conjugate are called

Hermitian Operators.

∞ ∗ ∞
∗ ∗
Ψ𝐻Ψ = න Ψ ∗ 𝑥 𝐻Ψ 𝑥 𝑑𝑥 = න Ψ 𝑥 𝐻Ψ 𝑥 𝑑𝑥 = 𝐻Ψ Ψ
−∞ −∞

⟹ 𝐻Ψ Ψ = Ψ 𝐻Ψ = 𝐻 † Ψ Ψ
⇒ 𝐻† = 𝐻
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Theorem: The eigenvalues of Hermitian operators are real.

Proof: Let Ψ be an eigenfunction of 𝐴መ with eigenvalue 𝑎:

መ = 𝑎Ψ
𝐴Ψ

መ ∗ Ψ𝑑𝑥 = ‫𝑎(׬‬Ψ)∗ Ψ𝑑𝑥 = 𝑎∗ ‫ ׬‬Ψ ∗ Ψ𝑑𝑥

Then we have, ‫𝐴(׬‬Ψ)
መ we also have
And by hermiticity of 𝐴,

መ ∗ Ψ𝑑𝑥 = න Ψ ∗ 𝐴Ψ𝑑𝑥
න(𝐴Ψ) መ = 𝑎 න Ψ ∗ Ψ𝑑𝑥

Hence, (𝑎∗ − 𝑎) ‫ ׬‬Ψ ∗ Ψ𝑑𝑥 = 0

And since, ‫ ׬‬Ψ ∗ Ψ𝑑𝑥 ≠ 0, we get, 𝑎∗ − 𝑎 = 0 ⇒ 𝑎∗ = 𝑎

The converse theorem also holds an operator is Hermitian if its

eigenvalues are real. The proof is left as an exercise.
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Unitary operator: An operator 𝐴መ is considered unitary if its adjoint equals its
inverse. Thus for a unitary operator,
𝐴መ ∗ = 𝐴መ −1 or 𝐴መ † = 𝐴መ −1
Or equivalently, 𝐴መ 𝐴መ † = 𝐴መ † 𝐴መ = 1
Laplacian Operator: The Laplacian operator is called an operator because it
produces or generates the sum of the three second-derivatives of the function.

2 𝜕2 𝜕2 𝜕2
It represented by ∇ = + + .
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

Hamiltonian Operator: The Hamiltonian operator operates on the

wavefunction to produce the energy, which is a number, (a quantity of Joules),
෡ 𝑟)ҧ = 𝐸 𝜓(𝑟)ҧ
times the wavefunction. 𝐻𝜓(
Hamiltonian Operator is the total energy operator consisting of the kinetic
energy operator plus the potential energy operator
ℏ2 2
෡=
𝐻 − 2𝑚 ∇ + 𝑉 𝑟ҧ = Hamiltonian operator
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Equal operator: The two operators say 𝐴መ and 𝐵෠ are called equal operators if
they operate on a function separately and produce the same result.

𝜕2 𝜕2
Ex : 𝑥2𝑦 = 2𝑥, 𝑥2𝑦 = 2𝑥
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥

𝜕2 𝜕2
Hence and are equal operator.
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥

Commutation of operator: Operators 𝐴መ and 𝐵෠ commute when

𝐴መ 𝐵Ψ
෠ 𝑥 = 𝐵෠ 𝐴Ψ መ 𝑥 ⇒ 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ Ψ 𝑥 = 0
𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ = [𝐴,
መ 𝐵]
෠ is called the commutation of the operators 𝐴መ and 𝐵.
෠

If 𝐴መ and 𝐵෠ are commute, then [𝐴,

መ 𝐵] መ 𝐵෠ ≠ 0
෠ = 0 otherwise, 𝐴,

𝜕2
Example: 𝐴መ = 5, 𝐵෠ = , Ψ 𝑥 = 𝑥 2 + 2𝑥
𝜕𝑥 2
𝜕2
𝐴መ 𝐵Ψ
෠ 𝑥 =5 2 (𝑥 2 + 2𝑥)= 5 × 2 = 10
𝜕𝑥
𝜕 2 𝜕2
መ 𝑥 =
𝐵෠ 𝐴Ψ 2
5(𝑥 + 2𝑥)= 2 (5𝑥 2 + 10𝑥) = 10
𝜕𝑥 2 𝜕𝑥
Hence, 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ = 0 and 𝐴መ and 𝐵෠ are said to be commute. 12
To find  and calculate the properties (observables) of a system:

1. Construct relevant operator 𝐴መ

መ = 𝑎Ψ
2. Set up equation 𝐴Ψ
3. Solve equation  allowed values of Ψ and 𝑎.

Quantum Mechanical Position and Momentum Operators

1. Operator for position in the x-direction is just multiplication by x

x̂ψ = xψ
  d
ˆ x = 
2. Operator for linear momentum in the x-direction: p
 i  dx
p̂ x ψ = p x ψ    dψ = p ψ
x
i dx
(solve first order differential equation   , px).
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We know the wavefunction, Ψ = 𝑒 −𝑖(𝜔𝑡−𝑘𝑥)
𝐸 𝑝
with the de Broglie relations telling us that 𝜔 = and 𝑘 =
ℏ ℏ

𝜕Ψ 𝑝
= 𝑖𝑘 𝑒 −𝑖(𝜔𝑡−𝑘𝑥) = 𝑖𝑘Ψ = 𝑖 Ψ
𝜕𝑥 ℏ

ℏ 𝜕Ψ
⟹ 𝑝Ψ = = momentum operator
𝑖 𝜕𝑥

Similarly, Its three-dimensional equivalent can be calculated:

Now, the wavefunction, Ψ = 𝑒 −𝑖(𝑘𝑟−𝜔𝑡)

𝜕Ψ 𝜕Ψ 𝜕Ψ
And the gradient is, ∇Ψ = 𝑒𝑥 + 𝑒𝑦 + 𝑒𝑧
𝜕𝑥 𝜕𝑦 𝜕𝑧
= 𝑖𝑘𝑥 Ψ𝑒𝑥 + 𝑖𝑘𝑦 Ψ𝑒𝑦 + 𝑖𝑘𝑧 Ψ𝑒𝑧
𝑖 𝑖
෠
= (𝑝𝑥 𝑒𝑥 + 𝑝𝑥 𝑒𝑥 + 𝑝𝑥 𝑒𝑥 )Ψ = 𝑃Ψ
ℏ ℏ
Where 𝑒𝑥 , 𝑒𝑦 and 𝑒𝑧 are the unit vectors for the three spatial
dimensions.
Hence, 𝑃෠ = −𝑖ℏ∇ 14
Constructing Kinetic and Potential Energy QM Operators
1. Write down classical expression in terms of position and momentum.
2. Introduce QM operators for position and momentum.

Examples
1. Kinetic Energy Operator in 1-D T̂x
ˆ 2 2  
px2 ˆ = p  d 2
CM Tx =  QM T x
=−  
2m  dx 2 
x
2m 2m 
2. KE Operator in 3-D T̂
CM QM “del-squared”

ˆ 2  
p2 px2 + py2 + pz2 ˆ = p 2
   2
 2
 2
=−  2
T= = T =− + 2 + 2 2
2m 
2m  x 2
y z  2m
2m 2m 

partial derivatives
operate on (x,y,z)

3. Potential Energy Operator V̂ (a function of position)

 PE operator corresponds to multiplication by V(x), V(x,y,z) etc. 15
4.2 The Schrödinger Equation (1926)

Schrödinger Equation is a mathematical expression that describes the

change of a physical quantity over time in which the quantum effects like
wave-particle duality are significant. The Schrödinger Equation has two
forms: the time-dependent Schrödinger Equation and the time-
independent Schrödinger Equation.

The central equation in Quantum Mechanics.

Observable = total energy of the system.

Schrödinger Equation Ĥψ = Eψ Ĥ Hamiltonian Operator

E Total Energy
where ˆ =T
H ˆ +V
ˆ and E = T + V.

• SE can be set up for any physical system.

• The form of Ĥ depends on the system.
• Solve SE   and corresponding E. 16
Schrödinger Wave Equation Derivation (Time-Dependent)
Considering a complex plane wave: Ψ 𝑥, 𝑡 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡)
Now the Hamiltonian system is: 𝐻 = 𝑇 + 𝑉
Where ‘𝑉’ is the potential energy, and ‘𝑇’ is the kinetic energy. As we already know
that ‘𝐻’ is the total energy, we can rewrite the equation as: 𝐸 = 𝑃2 Τ2𝑚 + 𝑉(𝑥)
𝜕Ψ(𝑥,𝑡)
Now taking the derivatives, = −𝑖𝜔𝐴𝑒 𝑖 𝑘𝑥−𝑤𝑡 = −𝑖𝜔Ψ 𝑥, 𝑡
𝜕𝑡

𝜕 2 Ψ(𝑥, 𝑡)
2 = −𝑘 2 𝐴𝑒 𝑖 𝑘𝑥−𝑤𝑡
= −𝑘 2 Ψ 𝑥, 𝑡
𝜕𝑥
2𝜋ℏ 2𝜋 𝑃
We know that, 𝑃 = , 𝑘= , 𝑘=
𝜆 𝜆 ℏ
𝜕2 Ψ(𝑥,𝑡) 𝑃2
Therefore, 𝜕𝑥 2 = − ℏ2 Ψ 𝑥, 𝑡
Now multiplying Ψ 𝑥, 𝑡 to the Hamiltonian we get,
𝑃2
𝐸Ψ 𝑥, 𝑡 = Ψ 𝑥, 𝑡 + 𝑉(𝑥)Ψ(𝑥, 𝑡)
2𝑚
The above expression can be written as:
ℏ2 𝜕 2 Ψ
𝐸Ψ 𝑥, 𝑡 = − + 𝑉(𝑥)Ψ(𝑥, 𝑡)
2𝑚 𝜕𝑥 2 17
We already know that the energy wave of a matter wave is
written as,
𝐸 = ℏ𝜔
So we can say that
ℏ𝜔 𝜕Ψ 𝜕Ψ(𝑥, 𝑡)
𝐸Ψ 𝑥, 𝑡 = = 𝑖ℏ
−𝑖𝜔 𝜕𝑡 𝜕𝑡
Now combining the right parts,
𝜕Ψ(𝑥,𝑡) ℏ2 𝜕 2 Ψ
𝑖ℏ = − + 𝑉(𝑥)Ψ(𝑥, 𝑡)
𝜕𝑡 2𝑚 𝜕𝑥 2
[time-dependent Schrödinger equation in 1D]
This is the derivation of Schrödinger Wave Equation (time-
dependent).
ҧ
𝜕Ψ(𝑟,𝑡) ℏ2 2
𝑖ℏ = [− ∇ + 𝑉 𝑟ҧ ]Ψ(𝑟,ҧ 𝑡)
𝜕𝑡 2𝑚
[time-dependent Schrödinger equation in 3D]
18
The energy is a constant for conservative systems, and the time-dependent
factor from 3D equation can be separated from the space-only factor.
ҧ −𝑖𝐸𝑡/ℏ
Ψ 𝑟,ҧ 𝑡 = 𝜓(𝑟)𝑒
where 𝜓(𝑟)ҧ is a wavefunction dependent (or time-independent) wave function
that only depends on space coordinates. Putting this Equation into time-
dependent Schrödinger equation in 3D and canceling the exponential factors, we
obtain the time-independent Schrödinger equation:
ℏ2 2
− ∇ + 𝑉 𝑟ҧ 𝜓(𝑟)ҧ = 𝐸 𝜓(𝑟)ҧ
2𝑚
[time-independent Schrödinger equation]
ℏ2 2
෡
𝐻 = − ∇ + 𝑉 𝑟ҧ = Hamiltonian operator
2𝑚

So time-independent Schrödinger Equation can then be simplified as

෡ 𝑟)ҧ = 𝐸 𝜓(𝑟)ҧ = eigenvalue equation

𝐻𝜓(
𝜓(𝑟)ҧ = eigenvalue function
𝐸 = eigenvalue
Hamiltonian operator operates on the wavefunction to produce the energy, which
is a scalar times the wavefunction.
19