BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 8
Quantum Theory - Foundation
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 Quantum Theory
Review of Lecture 7
Theoretical Explanations of (i) Spectrum of Blackbody
(Planck); (ii) Heat Capacity of Monoatomic Solids (Einstein);
(iii) Line Spectra of Hydrogen-like atom (Bohr’s Model)

Consequences: Quantization - Particle- character of Light

Verified by Photoelectric Effect (Einstein: Photons)
Wave-Particle duality of light

de Broglie postulated: Wave-character of Matter – Established

by Davisson & Germer Expt.
Wave-Particle Duality of “Entity”

Complementarity

Uncertainty Principle
2
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Young’s Double Slit Experiment

The same physical system can exhibit under different circumstances,

either particle or wave-like properties.
Experiment with Electrons:
Arrive in identical discrete lumps – particles
but distribution shows interference
We “cannot look” from which slit electron passes through and assume
that in some sense each electron passes through both slits. [Interference
Pattern]

Any experiment that can be devised that attempts to determine which

slit electron passes through always results in the disappearance of the
interference pattern

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Young’s Double Slit Experiment Contd…

Detector On
No Interference

Detector Off

Interference

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De Broglie Matter Waves
Every particle has a wave associated with it.

Wave in quantum mechanics are “Probability Waves”.

There are “entities or (objects)” which may behave like a wave or a

particle but never simultaneously as both. (Complementary)

A stronger manifestation of the particle nature leads to a weaker

manifestation of the wave nature and vice versa.

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Wave-Particle Duality
Waves-Nature: Waves are spread out, like the pure sine wave shown
below

Particle-Nature: Particles are localized; they have a definite location, like

the particle shown below.

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Particle-Nature of an Entity

Adding together several pure sine waves with different wavelengths

produces a resultant wave that is somewhat localized. The more sine
waves you add together, the more the resultant wave will be localized,
and the less uncertainty there will be about the object's location.

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Wave-Particle Duality
Waves-Nature:
A pure sine wave has a precise wavelength, and so the object represented
by a sine wave has a precise momentum. But a pure sine wave keeps
going forever in both directions; it is not at all localized. Therefore we
are perfectly uncertain about where the object is!

Particle-Nature:
What is the momentum of the object represented by the resultant wave?
The resultant wave contains a spread of wavelengths (the wavelengths of
the sine waves), and it is not clear which wavelength goes into de
Broglie's formula. Thus there is some uncertainty about the object's
momentum. If you add more sine waves together, the resultant wave will
be more localized, but there will also be more of an uncertainty in the
wavelength and momentum of the object represented by the resultant
wave.
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Uncertainty Principle
Werner Heisenberg - Wave-particle duality of nature – “there is a
natural tradeoff between knowing an object's position and knowing
it's momentum”.

It is impossible to predict, measure, or know both the exact position of

an object and its exact momentum at the same time. In fact, an
object does not have an exact position and momentum at the same
time! Heisenberg uncertainty principle

px x  ħ/2

It is a natural consequence of the wave-particle duality of nature.

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Quantum “Curtain”

“No one knows what happens behind the quantum curtain…

but we should not care!”

Interested in the outcomes of measurements

(only the results count… )
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Postulates of Quantum Mechanics
Quantum Mechanics: Based on several statements – Postulates
(Assumed)
Statements based on these assumptions lead to predictions that agree
with the observations
Ultimate goal is to have a theory that proposes how matter behaves and
predicts events that agree with observations

Why not describe the behavior of matter using an expression for a

wave?

Postulate 1: State of a system can be described by an expression called

wavefunction.
Physical meaning of wavefunction is difficult to describe. [Think of
wavefunction as a description of the system of interest and with this
description various properties of the system can be determined.]
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Wavefunction Ψ/ψ (PSI/psi)

The state of a system (entity) is completely specified by its

wavefunction (x, y, z, t), which is a probability amplitude and
has the significance that
2 dV
(more generally 2dV since  may be complex)
represents the probability that the particle is located in the
infinitesimal element of volume dV about the given point, at
time t

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Stationary States

In many situations of interest in chemistry, one is

concerned with stationary states, for which the
probability distribution is independent of time. For such
states,
2 dV
represents the (time-independent) probability
distribution, where the wavefunction (x,y,z) is a
function of the spatial coordinates alone

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Wavefunction Ψ/ψ (PSI/psi)

For various physical and mathematical reasons, these

wavefunctions are limited to being functions that are
• must be single valued

• must be continuous

• d/dx is continuous

• all space n2 dx must be finite, ie.,  must be normalizable

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Born Interpretation of the wavefunctions
Interpret the wavefunction in terms of “probability of location” of the
particle

Wavefunction is probability amplitude and square of the wavefunction is

probability density

If the wavefunction of a particle has a value ψ at some point r, then the

probability of finding the particle in an infinitesimal volume dτ = dxdydz
at that point is proportional to |ψ|2d τ

The Born Interpretation makes the necessity of wavefunctions being

bounded and Single-Valued

The Born Interpretation also suggests that wavefunction are expected to

be Normalized
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Normalization
If the probability for a particle having wavefunction ψ were
evaluated over the entire space in which the particle exists, then
the probabilty should be equal to 1.
all space 2 dτ = 1

The wavefunction must be multiplied by some constant so that

the area under the curve 2 is equal to 1.

The normalization does not affect the shape of the function, it

imposes a scaling factor on the amplitude

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Wavefunction Ψ/ψ (PSI/psi)
Single valued requires that there be a single value of the function
for a given interval.

Not single valued Single valued

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Wavefunction Ψ/ψ (PSI/psi)
Continuous requires that the function and the first-derivative of
the function be smoothly varying with no discontinuities

Not Continuous Continuous

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Wavefunction Ψ/ψ (PSI/psi)
Normalization Requires

all space 2 dτ = 1

Tan x? Not good.

Sin x? Good.

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“Observables”
Postulate 1: State of a system can be described by an expression
called wavefunction. All the possible information about the various
observable properties must be derived from the wavefunction

What is an “Observable”?
When studying the state of a system, one typically makes various
measurements of its properties such as position, momentum, energy…

Each individual property is called an “Observable”

How does one determine the value of various observable from a

wavefunction?

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Postulate 2: Operator
To determine the value of an observable, some mathematical
operation should be performed on the wavefunction.
This operation is represented by an Operator.

Operator: “Mathematical Instruction”: “Do something to this

function or numbers”
An Operator acts on a function to give a result (which may be a
function/ constant)
Example: d/dx : operator; 3x2 + 2x : function; 6x + 2 : Result
d/dx (3x2 + 2x) = 6x +2

When an operator acts on a function, some other function is usually

generated.
There is a special type of operator-function combination that when
evaluated produces some constant(s) times the original function
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 Eigen value equation

ÂΦ=KΦ
K = Eigen Value
Φ is the Eigen function of the operator Â

Note: Not all functions are Eigen functions of all operators

Solution: if y = eax then,

dx
   
d ax
e ae ax

Eigen value r = a;
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 Postulate 2 contd…
bservable
For everyinmeasurable
quantum mechanics
property is(Observable)
represented byofantheoperator
system,which
there i
physical
exists a information
correspondingabout the observable from the state function.
operator.
ble
Allthat is represented
classical in classical
mechanical physics
properties havebyaacorresponding
function Q(x,p),Quantum
the corre
 
is Q( x, p) . operator.
mechanical
Observable Operator

Position x
Momentum   
p
i x
Energy 2
p  2 2
E  V ( x)    V ( x)
2m 2m x 2

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Postulate 3:
For any measurement involving an observable corresponding to an
operator, the only values that will be measured should be eigen values
of the operator.

Example: If you want to make measurements of a physical observable

(property) G of an entity; use the corresponding operator Ĝ; select a
well-behaved mathematical function;[represents the entity]
The operator-function combination should form eigen value equation
and the eigen value of the equation will be the value of that observable.

Not all experimental quantities are determined by any one wavefunction.

Rather, a given wavefunction is an eigen function of some operators by
not an eigen function of others.

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The Schrödinger Equation

One of the most important ideas in quantum mechanics is the

Schrödinger equation, which deals with the most important observable:
ENERGY
E (total Energy) = KE + PE
Corresponding Operator (Hamiltonian)
2 2 2
P  d
Hˆ   V (r )   2
 V (r )
2m 2m dx
2  2 2 2 
  2  2  2   V (r )
2m  x y z 
2 2
   V (r )
2m
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The Schrödinger equation

The wavefunction (for stationary states) satisfies the Schrodinger

equation Ĥ  = E 
where is called the Hamiltonian Ĥ operator, a set of well defined
operations to be carried out on the function , and ‘represents’ the
energy E. In one dimension, the Hamiltonian may be written as
Ĥ = -ħ2/2m d2/dx2 + V(x)
where V(x) is the potential energy to which the particle is subjected

Ĥ=E

 2  2 2 2  
  2  2  2   V (r ) ( x, y, z )  E ( x, y, z )
 2m  x y z  
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Applications

To find properties (Total energy) of entity according to

quantum mechanics; we need to solve the appropriate
Schrödinger equation

Solutions for three basic types of motion:

Translation, Vibration and rotation

Translational Motion: Particle in a 1D “box”

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 Particle in one dimensional box

• It is supposed that the

V(x) = 0 inside the box but
becomes infinity at x = 0
and L.
• According to the
interpretation of wave
functions, they should be
equal to zero at x = 0 and
L. These conditions are
called boundary
conditions.

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 Particle in one dimension box

Boundary conditions must be satisfied by the wave functions

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