General Chemistry (CHEM F111)

Lecture 4, 28-10-2022
Recap

Wave particle duality

de Broglie hypothesis
Wave function
Probability density and probability
Well-behaved wave functions
Normalization

 Thus wavefunctions need to be normalized

Wavefunctions are normalized if and only if



  
*
dx 1

Consider (x) = sin(2πx) with 0 ≤ x ≤1, probability would
be
1 1
P(x) = 0  2 dx =  sin2(2x) dx = 1/2
0

In order for the particle to exist in the given region

of space, the probability should be P(x) should be 1

In order to have 100% probability, we need to multiply the

wavefunction with a constant, then (x) = A sin(2πx)

1 1
P(x) = A2
0  2 dx = A2  sin2(2x) dx = 1
0
A = √2, Normalisation constant
 Usually the wavefunction is multiplied
with a constant so that normalization
condition can be satisfied

It doesn’t effect the shape of the function,

it only imposes a scaling factor on the amplitude
 Stationary States
In many situations of interest in chemistry, one is
concerned with stationary states.
the probability distribution is independent of time.
For such states,
ψ2 dV
represents the (time-independent) probability
distribution.
wavefunction ψ(x,y,z) is a function of the spatial
coordinates alone.
Eigenvalue equations

Eigen – Own or Characteristic

Operator: d/dx operating on e ax

ax
eigenfunction = e
Eigenvalue =a; dx
   
d ax
e  a e ax

Operator on function = constant × function

Observables : position, momentum, K.E, P.E etc
Operators : x, P, K, V, Ĥ etc. ̂x
 Most important operator in
Quantum Theory

Hamiltonian Operator, Ĥ
Operator corresponding to the Total energy

Total energy = KE + PE

p2
E   V ( x, t )
2m
The different steps to construct the Schrödinger equation
1. Write the classical mechanical expression
for total energy
1. Total energy = K.E + P.E
2. For eg. For a particle of mass m in one dimensions
1
E  mv x  V ( x)
2

2
2
Px
E  V ( x)
2m
Wherever x,y,z occur, leave them unchanged
Px ,Py , Pz etc. should be replaced with Px = - i h d
dx
ħ
22
d2
H   V ( x) ħ2
2m dx 2
 The Schrödinger Equation
Ĥψ=Eψ ‘Ĥ’ is Hamiltonian operator

Eigenvalue equation for the Hamiltonian

operator

(Total Energy operator) on (wavefunction)

= (total energy)*(wavefunction)
Ĥ - Operator for Total energy, E, of the system
2
p
E   V ( x, t )
2m
 Simple Applications

•Free particle
•Particle confined in a box
•Particle on a ring
•Particle on a sphere
•Harmonic oscillator

If we can solve Schrödinger equation, we

know everything about the system
 The Schrödinger Equation
Ĥψ=Eψ
‘Ĥ’ is Hamiltonian operator
When ψ is operated upon by Ĥ, returns the ψ
multiplied by E
2
Total energy = KE + PE p
E   V ( x, t )
2m
Px = -ihd
dx
2 2
-h d + V(x) x = Ex
2m dx2
Particle in a one dimensional box
Particle confined in one dimension

Practically interesting:
1. trapped electrons in a cavity in nanometer
sized structures in reality
2. Electrons in conjugated dienes
 Translation: Particle in a box
Consider a particle in one dimension confined to a length L
by infinite potential barriers at x = 0 and x = L (infinitely
deep potential well)

V= V=
V=

V=0 V=0
inside box inside box
 For regions I and III
Region I V Region II V Region III
ħ22 d2 (x)
V=  V=  V=  - 2  V(x) = E(x)
2m dx

X=0 X=l ħ22 d2 (x)

- 2  (x) = E(x)
2m dx

1 ħ22 d2 (x)
(x) =
 2m dx 2

For regions I and III ψ(x) = 0

Particle does not exist there

Region I V Region II V Region III

V=  V=  V= 

X=0 X=l

For region II :
ħ22 d2 (x)
- 2  V(x) = E(x)
2m dx For region II :
ħ22 d2 (x) d 2 ψ(x) 2mE
 2 ψ(x) = 0
- 2 = E(x) 2
2
2m dx dx ħ
d 2 ψ(x)
2
 k 2
ψ(x) = 0
dx
2mE
k  2
2

Ψ(x) = A sin(kx) + B cos(kx) ħ 2

Boundary Conditions – Quantization
Particle is confined 0xL.
Boundary condition 1. x ≤ 0 V(x) = ∞  = 0
2 . x ≥ L, V(x) = ∞ ,  = 0

Significance of boundary conditions

Only certain wavefunctions and energies

are acceptable

The motion is quantized

Region I V V d 2 ψ(x)
Region II Region III
2
 k 2
ψ(x) = 0
dx
V=  V=  V= 
2mE
k 
2

 22
X=0 X=l ħ
Ψ(x) = A sin(kx) + B cos(kx)
Apply boundary condition Ψ(0) =0 ; Ψ(L) = 0

Ψ(L) = A sin(kL) = 0 ; kL = nπ

nπ/L = (2mE)1/2 / ћ

n2h2 Ψ(x) = A sin(nπx/L)

Therefore
En  2
8mL
For x < 0 and x > L,  = 0 since probability of
finding the particle in these regions is zero.
For 0  x  L, the solution to the Schrodinger
equation is
(x) = A sin(nπx/L)

with k = (2mE)1/2/ħ
Normalized wavefunction/eigenfunction

n=1,2,3….

n can not be zero; then =0

everywhere and particle vanishes;
2 2
nh
Allowed Eigenvalues En  2
8mL
Energy levels are quantized