Nanophysics

Dr. Kazi Hanium Maria

Course Code: PHY 171
Course teacher

1
Recall
1. Particle Moving in 1-D (x)

ˆ ψ=T
ˆ ψ+V
ˆ ψ = Eψ  2   2 ψ 
H − + V(x )ψ = Eψ

2m  x  2 

• The form of V(x) depends on the physical situation:

– Free particle V(x) = 0 for all x.
– Harmonic oscillator V(x) = ½kx2

2. Particle Moving in 3-D (x,y,z)

 2   2 ψ  2 ψ  2 ψ 
• SE  − + 2 + 2 + V(x, y, z )ψ = Eψ

2m  x 2
y z 
2 2
or −  ψ + V(x, y, z )ψ = Eψ Note: The SE is a second order
2m differential equation
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 4.3 Application of SE equation: Particle in a 1-D Box
For a particle moving in one dimension (along the 𝑥-axis), the Schrödinger
equation can be written as:
ℏ2 𝜕2 Ψ(𝑥)
− + 𝑉 𝑥 Ψ 𝑥 = 𝐸Ψ(𝑥)………..(1)
2𝑚 𝜕𝑥 2

Boundary condition: Assume that the

particle can move freely between two
endpoints 𝑥 = 0 and 𝑥 = 𝐿, but cannot
penetrate through any end. Therefore,
potential energy dependent on 𝑥 with

𝑉 𝑥 = 0 0≤𝑥≤𝐿
∞ 𝑥<0 & 𝑥>𝐿

The infinite potential energy

constitutes an impenetrable barrier Figure: The barriers outside a one-
since the particle would have infinite dimensional box have infinitely large
potential energy which is impossible potential, while the interior of the box has
here. a constant, zero potential 3
Thus the particle is bound to a "potential well" since the particle cannot
penetrate beyond 𝑥 = 0 for or 𝑥 = 𝐿
Ψ 𝑥 = 0 for 𝑥 < 0 and 𝑥 > 𝐿
With this condition, the wavefunction is continuous for
Ψ 0 = 0 and Ψ 𝐿 = 0
which constitutes a pair of boundary conditions on the wavefunction
within the box.
Inside the box, 𝑉(𝑥) = 0, equation reduces to the free-particle form:
ℏ2 𝜕2 Ψ(𝑥)
− = 𝐸Ψ(𝑥) with 0 ≤ 𝑥 ≤ 𝐿 …………..(2)
2𝑚 𝜕𝑥 2

ℏ2 𝑘 2 2𝑚𝐸
Using, 𝐸 = ⇒ 𝑘2 = , the differential equation can be written as,
2𝑚 ℏ2

𝜕2 Ψ 𝑥 2𝑚𝐸 𝜕2 Ψ 𝑥
+ Ψ 𝑥 =0⇒ + 𝑘 2 Ψ 𝑥 = 0 ………..(3)
𝜕𝑥 2 ℏ2 𝜕𝑥 2

This is a second order differential equation. 4

The second-order differential equation has a general solution of the form:
Ψ 𝑥 = 𝐴𝑠𝑖𝑛𝑘𝑥 + 𝐵𝑐𝑜𝑠𝑘𝑥
Where A and B are constants which can be determined by applying the
B.C.: x = 0 Ψ 0 = 𝐴𝑠𝑖𝑛 0 + 𝐵𝑐𝑜𝑥 0 = 𝐵 = 0 ⇒ Ψ 𝑥 = 𝐴𝑠𝑖𝑛 𝑘𝑥
Now applying the second B.C.: x = 𝐿 into first B.C solved equation:
Ψ 𝐿 = 𝐴𝑠𝑖𝑛 𝑘𝐿 = 0

It is assumed that 𝐴 ≠ 0, Ψ 𝑥 would be zero everywhere and the particle

would disappear. The condition that 𝑠𝑖𝑛𝑘𝑥 = 0 implies that 𝑘𝐿 = 𝑛𝜋
Where n is a integer, positive, negative or zero.
𝑛𝜋
k is restricted to a discrete set of values: 𝑘 =
𝐿

ℏ2 𝜋 2 2 ℎ2 ℎ
With allowed energies, 𝐸𝑛 = 𝑛 = 𝑛2 [𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 ℏ = ]
2𝑚𝐿2 8𝑚𝐿 2 2𝜋

with n = 1, 2, 3,………quantum number

5
 The integer values of n are the allowed energy level for the solutions of the
Schrödinger Equation. Negative values of n add nothing new because the
energies depend on 𝑛2 .

Figure shows part of the energy-level diagram for the particle in a box. The
occurrence of discrete or quantized energy levels is characteristic of a bound
system, that is, one confined to a finite region in space. For the free particle, the
absence of confinement allowed an energy continuum. 6
The particle in a box assumes its lowest possible energy when 𝑛 = 1,
ℎ2
𝐸1 =
8𝑚𝐿2

The state of lowest energy for a quantum system is termed its ground state.
Therefore, the allowed wavefunctions: Ψ𝑛 (𝑥) = 𝐴𝑠𝑖𝑛(𝑛𝜋𝑥Τ𝐿)
𝑛𝜋
with 𝐵 = 0, 𝑘 = = 𝑎 and 𝑛 = 1, 2, 3, … … …
𝐿
The constant 𝐴 can be determined by normalized the wavefunction Ψ𝑛 (𝑥)
𝑎
The normalized condition is, ‫׬‬0 Ψ(𝑥) 2 𝑑𝑥 = 1
The integration running over the domain of the particle 0 ≤ 𝑥 ≤ 𝐿.
𝐿 𝑛𝜋
2 2
𝑛𝜋𝑥 2
𝐿 2 2
𝐿
𝐴 න 𝑠𝑖𝑛 𝑑𝑥 = 𝐴 න 𝑠𝑖𝑛 𝜃𝑑𝜃 = 𝐴 = 1
0 𝐿 𝑛𝜋 0 2
2
By substituting, 𝜃 = 𝑛𝜋𝑥Τ𝐿. Therefore, the normalization constant, 𝐴 =
𝐿
2
The normalized wavefunction, Ψ𝑛 (𝑥) = 𝑠𝑖𝑛(𝑛𝜋𝑥Τ𝐿)
𝐿
with 𝑛 = 1, 2, 3, … … …
7
Quantum Numbers

• There is a discrete energy state (En),

corresponding to a discrete wavefunction
(n), for each integer value of n.

• Quantization – occurs due to boundary

conditions and requirement for  to be
physically reasonable (Born interpretation).

• n is a Quantum Number – labels each

allowed state (n) of the system and
determines its energy (En).

• Knowing n, we can calculate n and En.

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Properties of the Wavefunction

 nx

• Wavefunctions are standing waves: ψn = 2
L
sin 
 L 

• The first 5 normalized wavefunctions for the particle in the 1-D

box:

• Successive functions possess one more half-wave ( they have a

shorter wavelength).

• Nodes in the wavefunction – points at which n = 0 (excluding the

ends which are constrained to be zero).

• Number of nodes = (n-1) 1 → 0; 2 → 1; 3 → 2 … 9

Curvature of the Wavefunction

• If y = f(x) dy/dx = gradient of y (with respect to x).

d2y/dx2 = curvature of y.

  2ψ 
• In QM Kinetic Energy  curvature of  T   2 + .....
 x 
 
• Higher curvature  (shorter )  higher KE

• For the particle in the 1-D box (V=0):

  2ψn  n2
KE E n = Tn   
 x 2  L2
 

10
 n 2h2
Energies En =
8mL 2

• En  n2/L2  En as n (more nodes in n)

En as L (shorter box)
n (or L)  curvature of n
 KE  En

E  E
2 node

L
1

L1 L2 11
• En  n2  energy levels get further apart as n
n E

9h 2
3 E3 =
8mL2

4h 2
2 E2 =
8mL2

h2
1 E1 = h2
8mL 2 ZPE =
0 8mL2

• Zero-Point Energy (ZPE) – lowest energy of particle in box:

h2
ZPE = E min = E 1 =
8mL2

• CM Emin = 0
• QM E = 0 corresponds to  = 0 everywhere (forbidden). 12
• If V(x) = V  0, everywhere in box, all energies are shifted by V.

V=0 V0
E2=E2+V
n 2h2
En = 2
+V E2
8mL
E1=E1+V
V
E1

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Density Distribution of the Particle in the 1-D Box

• The probability of finding the particle

between x and x+dx (in the state 
represented by n) is:
Pn(x) = n(x)2 dx = (n(x))2 dx (n is real)

2 nx  2
 Pn (x ) = 2
L
sin  dx
 L 

• Note: probability is not uniform

2
– n 0 at walls (x = 0, L) for all n.
2=

– n2 = 0 at nodes (where n = 0).

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The patterns of
standing waves on
the string are, in
fact, identical in
form with the
wavefunctions

Fig: The probability density distribution Ψ𝑛 (𝑥) 2 for a quantum particle in a

box for: (a) the ground state, 𝑛 = 1; (b) the first excited state, 𝑛 = 2; and, (c)
the nineteenth excited state, 𝑛 = 20.
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4.4 Further Examples

(a) Particle in a 2-D Square or 3-D Cubic Box

• Similar to 1-D case, but  → (x,y) or (x,y,z).
• Solutions are now defined by 2 or 3 quantum numbers
e.g. [n,m, En,m]; [n,m,l, En,m,l].
• Wavefunctions can be represented as contour plots in 2-D

(b) Harmonic Oscillator

• Similar to particle in 1-D box, but PE V(x) = ½kx2

(c) Electron in an Atom or Molecule

T̂ 3-D KE operator

V̂ PE due to electrostatic interactions between electron and all

other electrons and nuclei. 16
 Postulates of Quantum Mechanics

Postulate 1: The Wave Function

The state of a quantum mechanical system is completely specified by a
function Ψ 𝑟, 𝑡 that depends on the coordinates of the particle(s) and on
time. This function is called the wave function or state function, has the
important property that Ψ ∗ (𝑟, 𝑡)Ψ 𝑟, 𝑡 𝑑𝜏 is the probability that the particle
lies in the volume element 𝑑𝜏 located at 𝑟 at time 𝑡.

The wavefunction must satisfy certain mathematical conditions because of

this probabilistic interpretation. For the case of a single particle, the
probability of finding it somewhere is 1, so we have the normalization
condition.

∞
‫׬‬−∞ Ψ ∗ 𝑟, 𝑡 Ψ 𝑟, 𝑡 𝑑𝜏 = 1

It is customary to also normalize many-particle wavefunctions to 1. The

wavefunction must also be single-valued, continuous, and finite.
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 Postulate 2: Experimental Observables
To every observable in classical mechanics, there corresponds a linear
Hermitian operator in quantum mechanics. This postulate comes from
the observation that the expectation value of an operator that
corresponds to an observable must be real and therefore the operator
must be Hermitian. Some examples of Hermitian operators are:

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Postulate 3: Individual Measurements

In any measurement of the observable associated with operator 𝐴መ , the only

values that will ever be observed are the eigenvalues 𝑎 that satisfy the
መ 𝑥 = 𝛼Ψ(𝑥)
eigenvalue equation: 𝐴Ψ

This postulate captures the central point of quantum mechanics: the values
of dynamical variables can be quantized (although it is still possible to have a
continuum of eigenvalues in the case of unbound states). If the system is in
an eigenstate of 𝐴መ with eigenvalue 𝑎, then any measurement of the quantity
𝐴 will yield 𝑎. Although measurements must always yield an eigenvalue, the
state does not have to be an eigenstate of 𝐴መ initially.

An arbitrary state can be expanded in the complete set of eigenvectors of

𝐴መ (𝐴Ψ
መ 𝑥 = 𝛼Ψ(𝑥)) as:
Ψ = σ𝑛𝑖 𝑐𝑖 Ψ𝑖

where 𝑛 may go to infinity. In this case, we only know that the measurement
of A will yield one of the values 𝑎𝑖 , but we don’t know which one.

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Postulate 4:Expectation Values and Collapse of the Wavefunction

If a system is in a state described by a normalized wave function Ψ,

then the average value of the observable corresponding to 𝐴መ is given
by
∞
መ
𝐴 = න Ψ ∗ 𝐴Ψ𝑑𝜏
−∞

Postulate 5: Time Evolution

A system’s wavefunction or state function evolves in time according to
the time-dependent Schrödinger equation.

෡ 𝑟, 𝑡 = 𝑖ℏ 𝜕Ψ
𝐻Ψ
𝜕𝑡

The central equation of quantum mechanics must be accepted as a

postulate.

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Postulate 6: Pauli Exclusion Principle
The total wave function of a system with N (spin-1/2) particles (also
called fermions) must be antisymmetric with respect to the interchange
of all coordinates of one particle with those of another. For spin-1
particles (also called bosons), the wave function is symmetric:
Ψ 𝑟1 , 𝑟2 , … … … … 𝑟𝑁 = −Ψ 𝑟2 , 𝑟1 , … … . 𝑟𝑁 = 𝐹𝑒𝑟𝑚𝑖𝑜𝑛𝑠
Ψ 𝑟1 , 𝑟2 , … … … … 𝑟𝑁 = +Ψ 𝑟2 , 𝑟1 , … … . 𝑟𝑁 = 𝐵𝑜𝑠𝑜𝑛𝑠

Electronic spin must be included in this set of coordinates. The

mathematical treatment of the antisymmetric postulate gives rise to the
Pauli exclusion principle, which states that two or more identical
fermions cannot occupy the same quantum state simultaneously (while
bosons are perfectly capable of doing so).
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 Concluding Remark:

QM has been an unqualified success

in quantitatively describing the
atomic and sub-atomic world, its
interpretative aspects have not
been satisfactory.

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THANKS..

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