BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 2

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Summary (Lecture 1)
Classical Mechanics: Failures to explain

Black body radiation (1860):

Plancks Explanation (1901-1909):
Energy quantized.
Photoelectric effect (1887):
Einstein Explanation (1905):
Particle character of light.
Energy Quantized
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Atomic Spectra: The phenomena

White light gets separated into its component colors after passing
through the prism.
When such a light is passed through hot gas/element, some
wavelength of light gets absorbed, while rest when analyzed
through spectroscope shows a series of characteristics lines at
definite wavelength: LINE SPECTRUM
Each element has its own
characteristics spectrum.
Complicated
elements

spectra

of

Comparatively simple spectra

for hydrogen.
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Mathematical explanation of Line Spectra of

Hydrogen Atom
Balmer (1885): Explained the lines in the visible region of
Hydrogen.
1
1
1
~
Positions of lines of light, wavenumber, R 2 2

2 n
n = 3, 4, 5. & R: some constant
Lyman (1)

Paschen (3)
Pfund (5)
Brackett (4)

Rydberg:Generalized Formula
1
1
1
~
RH 2 2

n1 n2

n1 and n2 (n2>n1) are positive

integers. (RH = 109737.315 cm-1)
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Bohrs Explanation: Model of Hydrogenlike Atom

Electron (mass m and charge e) moving in circular orbit of radius r
about nucleus of charge Ze;
mev2/r = Ze2/40r2
Bohr postulated that an electron can revolve around the nucleus only
in certain stable orbits without emitting any electromagnetic radiation.
(Electron must radiate energy, fall into the nucleus) [Classical Concept]

Only those orbits are stable for which the magnitude of

L (orbital angular momentum of the electron) is quantized.
L = mevr = nh/2 =n,
n=1,2,3,

0 h2n2
r
me e 2

quantization of angular momentum

Putting n = 1; r = a0 = 0.529 x 10-10 m;
First Bohr radius
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Bohrs Explanation on Line Spectra of

Hydrogen Atom
Transition between orbits are
allowed, but only when an
electron absorbs or emit a
photon of energy equal to the
difference between the energy
of the orbits. E h
~

E2 E1
hc

1me v 2
me e 4
e2
En KE V

2 2 2
2
4 0 r
8 0 h n
me e 4 1
1

E E2 E1 2 2 2 2
8 0 h n1 n2
4
1
m
e
1
v~ 2e 3 2 2
8 0 h c n1 n2

The equation
corresponds with the
me e 4
RH 2 3
experimentally
8 0 h c
observed result.
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Bohrs Model of Hydrogen-like Atom

Orbiting electrons existed in orbits
possessing discrete quantized energies
me e 4
13.6
En ( Hydrogen) 2 2 2
eV
2
8 0 h n
n

Bohr Model can make some approximate

predictions about the emission spectra for
atoms with a single outer-shell electron.
Z 2 me e 4 13.6Z 2
En 2 2 2
eV
2
8 0 h n
n

For example:
Be3+: Z = 4: single electron system
Limitation: Bohr Model cannot be applied to elements with more than
one electron
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Wave Character of Particles

If light (radiation) can be viewed as a collection of particles,
then can entities (particles) also be seen as waves ?

Davisson-Germer Experiment (1920-1925)

Scattering of electron beam
after interaction with single
crystal of nickel.

Series of bright and dark

fringes
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de Broglie (1924): Wave-particle duality

Just as light exhibits both wave-like (diffraction), and
particle-like characteristics, so should all material objects.
For light (photon)

E = pc (particle) = hc/ (wave)

p = h/

A particle with linear momentum p, has an associated

matter-wave of wave length ( and mathematical form
sin(2x/).

The Joint wave-particle character of matter and radiations is

called wave-particle duality.
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Wave-particle duality
The wavelength of the matter wave associated with a
particle should decrease as the particles speed increases
Lower p has a longer ;
Higher p has a shorter
.

Macroscopic objects are so massive that the de Broglie

wavelengths are immeasurably small, even if they travelling
slow.
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Uncertainty: A natural consequence

of wave-particle duality
A wave of wavelength
- corresponds to a particle with a constant p
-wave is spread through out the space.
-Precise location determination: Impossible.
A particle with fixed position (x)
-associated with wave of the form sin(2x/).
-Localized wavefunction(0) at x and 0 elsewhere.

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Uncertainty or Indeterminacy!
A
sharply
localized
wavefunction can be generated by
superposition of large no. of
wavefunctions. (resultant wave:
spread of waves of different
wavelengths)

Superposition of many waves

corresponds to superposition of
many different linear momenta.
(which of these wavelength should
fit into de broglie equation to give
momentum)

-Precise momentum determination: Impossible

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Heisenberg Uncertainty Principle

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! (Contrary to classical Mechanics)

px x /2

px : uncertainty in linear momentum

x : uncertainty in position

(a) (x: large) then (px : small)

(b) (x: small) then (px : large)

Complementary variables, increase in the precision of one

possible only at the cost of a loss of precision in the other.
Trajectories not defined precisely.
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Quantum Mechanics (QM): Discovery

Black Body Radiation
&
Line spectra of atoms
Atoms/molecules
exist with only
certain energies

De broglie duality
&
uncertainty principle

Davisson-Germer Exp.
&
Photoelectric Effect

Particle moving in precise

paths cannot have fixed
speeds.

Wave exhibit particle like

properties &
Particle exhibit wave like
properties

Quantum Mechanics:

A theoretical Science:
A particle is spread through space like wave. To describe this
distribution, a mathematical equation is required.
Wavefunction
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Wavefunction: / (PSI/psi)
Describing wave behavior of matter (any system) using an
expression of a wave: wavefunction [ ]
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) = (x,y,z) f(t)
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

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

2: Probability Density

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 =

dV
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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 d must be finite, ie., must be normalizable.

all space

2 d

= 1 or

2 d

=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 (x/2) for a system exist.

If the region of interest if from x= 0 to x = 1. Normalize the
function.

N (x) (Normalizable)

Solution: (x)(unnormalizable)
Such that

= N2

=1

= N2 [1/2] = 1 ;
Thus, (x)=

N=

sin (x/2) is now Normalizable

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Observables & Operators

A wavefunction should be defined in such a way that various
observable properties of the system can be determined.

y observable in quantum mechanics is represented by an operator which is use

Each individual property (x, p, E): An observable.
in physical information about the observable from the state function. For
rvable
is represented
in classical
physicsexist
by a function
Q(x,p),instruction)
the correspon
Forthat
every
observable:
an
Operator
(Mathematical

ator is Q( x, p) .
Observable

Operator

Position
Momentum

p
i x

Energy

2
p
2 2

E
V ( x)
V ( x)
2
2m
2m x
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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

Multiplication operator: M (2,3) = 2 x 3 = 6

Differentiation operator: D [F(x)] = d/dx (9x2+8x) = 18x+8

Momentum of a system = p [F(x)] =

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[F(x)]

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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:
Let the operator corresponding to a observable be : A
A =K

K = constant = Eigen Value

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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