Lecture # 3

Recap:
1. Schrodinger’s Equation: Wave-like equation

2. Born Interpretation for what y(x,t) is ?

3. Laws of QM

4. Concepts:
1. Normalization of Y(x,t) ---Restrictions on y(x,t)
2. Acceptable Y(x,t) (author of quantization---you will see)
3. Average/Expectation Value:

2
5. Probability = Y(x,t) dx = Y* (xa ,t)× Y(xa ,t)dx
 Math-3. Probability Distributions: Expectation (Average/Mean
value) and Most-Probable Value

If P(x) is the probability distribution

dP( x)
Most Probable (Modal) value at Maxima  0
dx
n n
Mean : E ( x)  x   x j Pj ( x j ) and E ( x 2 )  x 2   x 2j Pj ( x j )
j 1 j 1
 6. Normalization of Wavefunction

Since Ψ*Ψdτ is the probability, the total probability Ψ

∞ ∞
of finding the particle somewhere in space has to be
unity

 Y * ( x, y, z ).Y ( x, y, z )dxdydz

∞
x

all space ∞

 
all space
Y *Yd  Y Y  1
If function diverges, i.e.  ∞: Ψ can not be
Ψ
normalized, and therefore is NOT an acceptable
x
wave function. However, a constant value C ≠ 1 is
perfectly acceptable. Unacceptable wavefunction

Ψ must vanish at ±∞, or more appropriately at the boundaries and Ψ

must be finite
 Restrictions on wavefunction

ψ must be a solution of the Schrodinger equation

ψ must be normalizable: ψ must be finite and 0 at boundaries/

±∞

Ψ must be a continuous function of x,y,z

dΨ/dq must be must be continuous in q

Ψ must be single-valued

Ψ must be quadratically-intergrable
(square of the wavefunction should be integrable)

Origin of quantization
 Restrictions on wavefunction

Unacceptable because Unacceptable because

ψ is not continuous dψ/dq is not continuous

Unacceptable because Unacceptable because

ψ is not single-valued ψ goes to infinity
 Essence of Quantum Mechanics

• Not deterministic: Can not precisely determine many

parameters in the system, but Ψ can provide all the information
(spatio-temporal) of a system.

• Only average values and probabilities can be obtained for

classical variables, now in new form of “operators”.

• Total energy is conserved, but quantization of energy levels

come spontaneously from restriction on wave function or
boundary condition

• Final outputs tally very well with experimental results, and does
not violate Classical mechanics for large value of mass.
 Quantum Mechanics

Examples of Exactly Solvable Systems using

Schrodinger Equation

1. Free Particle
2. Particle in a Square-Well Potential
3. Hydrogen Atom

(xe,ye,ze)
 Recap: Restrictions on wavefunction

ψ must be a solution of the Schrodinger equation

ψ must be normalizable: ψ must be finite and 0 at

boundaries/ ±∞

Ψ must be a continuous function of x,y,z

dΨ/dq must be must be continuous in x,y,z

Ψ must be single-valued

Ψ must be quadratically-intergrable
(square of the wavefunction should be integrable)

Boundary conditions: Quantization

Free Particle

Time-independent Schrodinger equation

For a free particle V(x)=0

There are no external forces acting
Free Particle
m
x

Second-order linear differential equation

Let us assume
y ( x )  A sin kx  B cos kx Trial Solution

y ( x )  A sin kx  B cos kx
 
y ( x )   A sin kx  B cos kx   k  A cos kx  B sin kx 
dx dx
2
2
y ( x )   k 2
 A sin kx  B cos kx    k 2
y (x)
dx
Free Particle
m
x

Second-order linear differential equation

Let us assume
y ( x )  A sin kx  B cos kx Trial Solution

y (x) = Asinkx + Bcoskx

¶ ¶
dx
y (x) =
dx
( ) (
Asinkx + Bcoskx = k Acoskx - Bsinkx )
¶2
dx 2
y (x) = -k 2
(
Asinkx + )
Bcoskx = -k 2
y (x)
Free Particle
m
x
Free Particle
m
2
2
x
 y ( x )  E y ( x )
2m x 2
de Broglie wave
2 2
k2 2mE
k y ( x )  E y ( x )
2
 E  k
2m 2m

There are no restrictions on k

E can have any value
Energies of free particles are continuous

No Quantization All energies are allowed

Particle in 1-D Square-Well Potential

ì ¥ x <0
ï
V (x) = í 0 0£ x £ L
ï ¥ x>L
î

For regions in the space x < 0 and x > L  V = ∞

Normalization condition not satisfied 

y(x < 0) = 0 and y(x > L) = 0
Particle in 1-D Square-Well Potential

For regions in the space 0 ≤ x ≤ L  V = 0

This equation is similar to free particle Schrodinger

However, boundary conditions are present
Let is assume
y(x) = Asinkx + Bcoskx Trial Solution

Energy
Particle in 1-D Square-Well Potential

y(x) = Asinkx + Bcoskx

Boundary Condition x = 0 Þ y(x) = 0
y(x) = Asinkx ∵ cos0 = 1
Boundary Condition x = L Þ y(L) = 0
y(L) = 0 Þ AsinkL = 0 Þ A = 0 or sinkL = 0

But the wavefunction ψ(x) CANNOT be ZERO everywhere

sinkL = 0 Þ kL = np n=1,2,3,4...
Wavefunction is y(x) = Asinkx
Particle in 1-D Square-Well Potential

Energy is no longer continues but has

discrete values; Quantization of energy
Energy separation increases with
increasing values of n

The lowest allowed energy level is for n=1

has a non zero value  Zero Point Energy

Particle in 1-D Square-Well Potential: Spectroscopy

n2f h2 n2f h2
hn = DE = E f - Ei = 2
-
8mL 8mL2
= n -n (h2
8mL2
2
f
2
i )
Larger the box, smaller the energy of hν
Particle in 1-D Square-Well Potential

Wavefunction np
y (x) = Asinkx = Asin x
L

np
ò 0 y (x)× y(x)× dx = A ò
L * L
Normalization 2
sin2 x ×dx = 1
0 L

2 2 np
A= y (x) = sin x
L L L

Homework
Evaluate the above integral
Particle in 1-D Square-Well Potential: Spectroscopy

Wavefunction 2 np
y (x) = sin x
L L

n=1,3.. (odd)
Symmetric
(even function)

n=2,4.. (even)
Anti-Symmetric
(odd function)

Number of Nodes
(zero crossings) = n-1
Expectation values

x = ò y * ×x × y × dx

2 np 2 np
ò
L
= sin x×x× sin x × dx
0 L L L L

2 np
ò
L
= x × sin
2
x × dx
L 0 L

L
=
2
Homework
Verify!
Expectation values

Homework
Verify!
Particle in 2-D Square-Well Potential

Hamiltonian

Let us assume that

y (x,y) = y (x)× y (y)
Particle in 2-D Square-Well Potential

= y (y)× Ex × y (x)+ y (x)× Ey × y (y)

= Ex × y (x)× y (y)+ Ey × y (x)× y (y)

( )(
= Ex + Ey × y (x)× y (y) )
= (E x
+ E ) × (y (x,y))
y
Particle in 2-D Square-Well Potential

Hamiltonian

y(x,y) = y(x)× y(y)

En = En ,n
= En + En
x y x y

ψ is a product of the eigenfunctions of the parts of Ĥ

E is sum of the eigenvalues of the parts of Ĥ

Particle in 2-D Square-Well Potential

y (x,y) = y (x)× y (y) V=0

2 np 2 np Ly
= sin x× sin y
Lx Lx Ly Ly
2 np np Lx
= sin x × sin y
Lx Ly Lx Ly

En ,ny
= En + En
x x y

nh 2 2
ny2h2
= x
2
+
8mL x
8mL2y
æ n2 n2 ö
2
h ç x y ÷
= + nx ,ny = 1,2,3,4...
8m çè Lx Ly ÷ø
2 2
Particle in 2-D Square-Well Potential

V=0
y (x,y) = y (x)× y (y)
Ly
2 np 2 np
= sin x× sin y
L L L L
2 np np Lx
= sin x × sin y
L L L Square Box
 L x = Ly = L

En ,n
= En + En
x y x y

nx2h2 ny2h2
= +
8mL 8mL2 2

=
h2
8mL 2
n 2
x
+ n(
y
2
) nx ,ny = 1,2,3,4...
Particle in 2-D Square-Well Potential

2 p 2p V=0
y1,2 = y1 × y2 = sin x × sin y
L L L Ly
5h2
E1,2 = E1 + E2 =
8mL2
Lx
2 2p p Square Box
y2,1 = y2 × y1 = sin x × sin y  L x = Ly = L
L L L
5h2
E2,1 = E2 + E1 =
8mL2

E1,2 = E2,1  y1,2 and y2,1 are degenerate wavefunctions

 Particle in 2-D Square-Well Potential – Symmetry

V=0 V=0
Ly Ly

Lx Lx

(1,3)
(3,1) (1,3)
(3,2)
(2,2)
(2,2) (1,2)
(3,1)
(2,1) (1,2) (2,1)
(1,1) (1,1)
Particle in a 2-D Well – Wavefunctions

Number of nodes = nx+ny-2

Particle in a 3D-Box

y (x,y,z) = y (x)× y (y)× y (z)

2 nx p 2 nyp
2 nz p
= sin x× sin y× sin z
Lx Lx Ly Ly Lz Lz
En ,n ,n
= En + En + En
x y z x y z

nx2h2 ny2h2 nz2h2

= 2
+ 2
+ 2
nx ,ny ,nz = 1,2,3,4...
8mL x
8mL y
8mL z
 Particle in a Box – Application in Chemistry

Hexatriene is a linear molecule of length 7.3 Å

It absorbs at 258 nm
Use particle in a box model to explain the results.

( )
2
h hc
DE = E f - Ei = n f - ni
2 2
=
8mL 2
l


l=
8mL2c 2
h
( )
n f - ni2 » 251nm

 Agrees well with the experimental

 value of 258 nm
Six  electron fill Particle in a box is a good model
lower three levels
Particle in a Box – Application in Chemistry

Electronic spectra of conjugated molecules

hc h2
= Þ l µ L2
l 8mL2
Increase in bridge length increase the
emission wavelength.
Predicts correct trend and gets the
wavelength almost right.
Particle in a box is a good model

Β-carotene is orange because of 11

conjugated double bonds
What have we learnt?
Formulate a correct Hamiltonian
(energy) Operator H

Solve TISE HY=E Y

by separation of variables and
intelligent trial wavefunction

Impose boundary conditions for

eigenfunctions and obtain
Quantum numbers

Eigenstates or Wavefunctions:
Should be “well behaved” -
Normalization of Wavefunction

Probabilities and Expectation Values