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CHEM F111 General Chemistry Lecture 03
Applications of Quantum Mechanics

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Review of Lecture 2
Origin of Quantum Mechanics
Photoelectric effect-Phenomena 2
-Einstein Explanation based on Quantization
Line Spectra of Hydrogen Atom-Phenomena 3
-Bohr Explanation based on Quantization
Wave-particle duality
- de Broglie Compilation on wave and particle nature of matter
Heisenberg Uncertainty Principle
- A natural consequence of wave-particle duality

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Quantum Mechanics (QM): Discovery
Black Body Radiation De broglie duality Davisson-Germer Exp.
& & &
Line spectra of atoms uncertainty principle Photoelectric Effect
Particle moving in precise
Atoms/molecules paths cannot have fixed Wave exhibit particle-like
exist with only speeds. properties &
certain energies Particle exhibit wave-like
properties
Quantum Mechanics:
A theoretical Science:
• A particle is spread through space like wave. To describe this
wave behavior, a mathematical equation is required.
Wavefunction
Describing wave behavior of electron (any microscopic
system) using an expression of a wave: wavefunction [ ]
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 Wavefunction: /ψ (PSI/psi)
 In QM, a particle is not localized. Approximately, wavefunction is a
blurred version of path.

 At any particular instance of time:  should depend upon (x,y,z,t)

 (state of a system): time dependent wavefunction
 (x,y,z,t) = ψ(x,y,z) f(t)
ψ is time-independent wavefunction, (wavefunction for a stationary
State)
 Wavefunction determines the probability distribution of finding
the particle at a point at any instance.
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 Wavefunction: Born Interpretation

•  could not be used as an indication of specific path of an electron.

• It is difficult to establish that a particular particle (electron) is in a

particular space at a particular time.

• Rather, over a period of time, the particle has a certain probability

(P) of being in a certain region (between two points a & b).

: Probability Amplitude: SHOULD NOT HAVE ANY

PHYSICAL SIGNIFICANCE

 2: Probability Density: SHOULD BE MORE SIGNIFICANT

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Wavefunction: Born Interpretation

• Probability that the particle is located in the infinitesimal element

of volume dV about the given point, at time t =  2dV

Total Probability between a & b =

P= * dV = 2 dV

 * complex conjugate of 

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Characteristics of Wavefunction:
Only those wavefunctions which follow the following criteria
are considered acceptable wavefunctions:
•  must be single valued & Bounded (Born Interpretation)
•  and d/dx must be continuous

• all space 2 dτ must be finite, ie.,  must be normalizable.

 all space 2 dτ = 1 or
2 dτ =1
(Born Interpretation)
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Normalization
If the given wavefunction is not normalize: we could make it
normalize by multiplying it by any constant and integrating
over its limits and determine the value of Normalization
constant.
Question: The wavefunction  (x)= sin (πx/2) for a system exist.
If the region of interest if from x= 0 to x = 1. Normalize the
function.
Solution:  (x)(unnormalizable) N (x) (Normalizable)
Such that * = N2 =1

= N2 [1/2] = 1 ; N=

Thus,  (x)= sin (πx/2) is now Normalizable

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 Observables & Operators
• A wavefunction should be defined in such a way that various
observable in quantum mechanics is represented by an operator which is used
observable
physical properties
information aboutofthe
theobservable
system can be the
from determined.
state function. For a
able that is Each individual
represented property
in classical physics(x,
byp, E): An observable.
a function Q(x,p), the correspondin
 
or isFor , p) . observable: an Operator exist (Mathematical instruction)
Q( xevery
Observable Operator

Position x
Momentum   
p
i x
Energy 2
p  2 2
E  V (x)    V ( x) ………..In 1-D
2m 2m x 2

E (total Energy) = KE + PE = mv2/2 + V = p2/2m + V

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 System Information from
observables
For determining values of observables: perform mathematical
operation (operator) on the wavefunction.
Observable operator acts on a function to give information
about the property
Differentiation operator: D [F(x)] = d/dx (9x2+8x) = 18x+8
Momentum of a system = p [F(x)] = [F(x)]
p2 2 d 2
Energy Operator : Hamiltonian ( H ) operator  V   2
 V ( x)
2m 2m dx………..In 1-D
2  2 2 2  2 2
H   2  2  2   V ( x, y, z )    V ………..In 3-D
2m  x y z  2m Cartesian
coordinates
Laplacian operator

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Eigen value Function
Special type of operator-function combination:
Operator when operated on function gives some constant(s)
times the original function: Eigen function of operator
Let the function defining a system be: Φ
Let the operator corresponding to a observable be : A
AΦ = KΦ K = constant = Eigen Value
Φ is the Eigen function of the operator.

 Not all functions are Eigen functions of all operators.

 Only those physical properties are determined by function if
that wavefunction is an eigen function of the corresponding
operator.
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Use of Eigen value Function
For determining the value of an observable (property, e.g. p, E)
for a physical system:
-Operate the operator (p, E) on well-behaved wavefunction (ψ)
of that system.
-This operator-function combination should form eigen value
equation and the corresponding eigen value = value of that
observable.
• Information about the system could only be known if we know the
eigen value of observable.

• A given wavefunction is an eigen function of some operators by not

an eigen function of others.
• Not all observables are determined by any one wavefunction.

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 Time-independent Schrödinger Eq.
• Energy of a system could be known by operating total energy
operator on the wavefunction.
• The wavefunction  (for stationary states; independent of time)
satisfies the Schrödinger equation:
Ĥ = E

 2  2 2 2  
  2  2  2   V ( x, y, z ) ( x, y, z )  E ( x, y, z )
 2m  x y z  
When  is operated upon by Ĥ, returns the  multiplied by E; a
category of equation called eigen (=own) value eqn.
Second order differential equation: the solutions will provide the
energies of possible states
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Next What ?

? How to extract information from the solutions

? How to solve schrödinger equation for the system
? How to define wavefunction of any system ?
 General form of Schrödinger Equation
 Observables & Operators
 Acceptable wavefunction
 Need for Quantum Mechanics

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