MODULE-I

INTRODUCTION TO ATOMIC

4/27/20
STRUCTURE

General Chemistry

1 CHY-111
 CONTENTS

Structure of the Atom,

4/27/20
Introduction to Periodic Table,
Evolution of Atomic Theory,
Thomson’s plum pudding model, Rutherford’s and, Bohr’s models,

Sample footer
Rutherford-Geiger-Marsden Experiment,
Planck-Einstein Relationship, Black body radiation, Planck’s constant;
Bohr’s postulates;
Matter-Energy interactions involving hydrogen atom;
quantum states; electron orbital transitions; s, p, d, f, orbital's;
electronic configuration based on quantum states;
Bohr-Sommerfield Model, Quantum numbers;
Balmer and Pfund Series, Rydberg Equation;
Stern-Gerlach Experiment;
Aufbau Principle; Pauli’s Exclusion Principle; Hund’s Rule;
Heisenberg’s Uncertainty Principle; Wave- Particle duality;
Schrodinger Equation; Simple Harmonic Oscillator; Particle in a Box. 2
 Structure of atom
 John Dalton (1805) considered that all matter was composed of
small particles called atoms.
He visualised the atom as a hard solid individual particle incapable

4/27/20
of subdivision.
At the end of the nineteenth century there accumulated enough
experimental evidence to show that the atom is made of still smaller

Sample footer
particles.
These subatomic particles are called the fundamental particles.
The number of subatomic particles now known is very large. For
us, the three most important are the proton, neutron and electron.
How these fundamental particles go to make the internal
structure of the atom, is a fascinating story.
The main landmarks in the evolution of atomic structure are :

1896 J.J. Thomson’s discovery of the electron

1909 Rutherford’s Nuclear Atom
1913 Mosley’s determination of Atomic Number
1913 Bohr Atom
1921 Bohr-Bury Scheme of Electronic Arrangement 3
1932 Chadwick’s discovery of the neutron.
4/27/20 Sample footer
4
 Structure of atom

In 1886, E. Goldstein discovered new radiations in gas discharge and called them canal
rays. These rays were positively charged. This later led to the discovery of the
positively charged particles called protons in the atom. In 1896, J.J. Thomson
discovered the presence of the negatively charged particles
called ELECTRONS in the atom.
In 1917, Ernest Rutherford discovered positively charged particle called Proton.

In 1932 Chadwick discovered the presence of particles having no charge in the atom
called neutrons

Subatomi Unit Unit Charge in Mass in

particle Symbol mass
c charge Coulom amu
s b
1 -19
1H +1.60 × 10 1.007825
Proton +1 1

1
0n 0
Neutron 1.008665
1 0

5
0
1 e
Electron -1 1.60 × 1019 5.489×10-4
Negligible
 INTRODUCTION TO PERIODIC TABLE
INTRODUCTION TO PERIODIC TABLE

THE PERIODIC LAW

Mendeleev understood the ‘Periodic Law’ which states:

 When arranged by increasing atomic number, the chemical elements display

a regular and repeating pattern of chemical and physical properties.

 Atoms with similar properties appear in groups or families

(vertical columns) on the periodic table.

 They are similar because they all have the same number of
valence (outer shell) electrons, which governs their chemical
behavior.
A DIFFERENT TYPE OF GROUPING
 Besides the 4 blocks of the table, there is
another way of classifying element:
 Metals

 Nonmetals

 Metalloids or Semi-metals.

 The following slide shows where each group is

found.
 METALS, NONMETALS, METALLOIDS

 There is a zig-zag
or staircase line
that divides the
table.

 Metals are on the

left of the line, in
blue.

 Nonmetals are on
the right of the line,
in orange.
 Noble Gas
Halogen
Group
Period
%
Alkali Earth Metal
Alkali Metal
PERIODIC PROPERTIES
 4/27/20 Sample footer
11
ATOMIC RADIUS
 Dalton’s Atomic Theory
Dalton’s Atomic Theory

Elements are made of extremely small

particles called atoms.

Atoms of a given element are identical in

size, mass, and other properties; atoms of

Sample footer
different elements differ in size, mass, and
other properties.

Atoms cannot be subdivided, created, or

destroyed.

Atoms of different elements combine in

simple whole-number ratios to form 
chemical compounds.

In chemical reactions, atoms are combined,

separated, or rearranged. 12

Dalton’s theory forms the foundation of Modern Theoretical

 Thomson model of an atom
 According to Thomson an atom is similar to a Christmas
pudding. The pudding had positive charge and the
electrons having negative charge were like plums on

4/27/20
the pudding.
 He proposed that :-
i) An atom consists of a positively charged sphere and
the electrons are embedded in it.
ii) The negative and positive charges are equal in
magnitude So the atom as a whole is electrically neutral

13
 Thomson’s Experiment

4/27/20
- +
Voltage
source

Sample footer
 Passing an electric current makes a beam appear to move from the
negative to the positive end
14

KS 14
 Thomson’s Experiment
Voltage source

4/27/20
+

Sample footer
-
 By adding an electric field he found that the moving pieces were
negative
15

KS 15
 Problems
Problemswith
withThomson’s
Thomson’sModel
Model

How does the atom emit radiation?

4/27/20
This model soon came into conflict with experiments by Rutherford

Sample footer
Rutherford-Geiger-Marsden gold foil experiment in 1909 disproved the
Plum Pudding Model and showed that instead of a soup of positive
charge, an atom consisted of a small nucleus of strong positive charge
paving the way to Rutherford’s Atomic Model.

16
 RUTHERFORD’S
RUTHERFORD’SMODEL
MODEL
Atom consist of two parts:

4/27/20
(a) Nucleus: Almost the whole mass of the atom is concentrated in this small
region

Sample footer
(b)Extra nuclear part: this is the space around the nucleus in which electrons are
revolving at high speeds in fixed path

17
Rutherford-Geiger-Marsden Experiment
Rutherford-Geiger-Marsden Experiment

4/27/20
18
 Rutherford model of atoms
Rutherford’s alpha scattering experiment :-

Rutherford allowed a beam of fast moving alpha particles ( α –particles)

4/27/20
having positive charge to fall on a thin gold foil. He observed that :-

Sample footer
i) Most of the α – particles passed straight through the gold foil.
ii) Some of the α – particles were slightly deflected by small angles.
iii) Very few α – particles appeared to rebound.

19
Based on these observations, Rutherford proposed a model
of the atom which is named after him. This is also called the

4/27/20
Nuclear Atom. According to it :

Atom has a tiny dense central core or the nucleus

Sample footer
which contains practically the entire mass of the
atom, leaving the rest of the atom almost empty. The
diameter of the nucleus is about 10-13 cm as compared to
that of the atom 10–8 cm.

The entire positive charge of the atom is located on

the nucleus, while electrons were distributed in
vacant space around it.

The electrons were moving in orbits or closed

circular paths around the nucleus like planets around
20
the sun.
 Defects
Defectsof
ofRutherford’s
Rutherford’smodel
modelof
ofthe
theatom
atom

 Any particle in a circular orbit would undergo acceleration and during

4/27/20
acceleration the charged particle would radiate energy. So the revolving
electrons would lose energy and fall into the nucleus and the atom would be
unstable. We know that atoms are stable.

Sample footer
Rutherford’s model of an atom

Negatively charged
electron
- -
Negatively charged
electrons in orbits
around the nucleus

+
-
Very small positively Positively charged
charged nucleus 21
nucleus
DEFINITION OF A BLACK BODY
DEFINITION OF A BLACK BODY

A black body is an ideal body which

allows the whole of the incident

4/27/20
radiation to pass into itself (without
reflecting the energy) and absorbs
within itself this whole incident

Sample footer
radiation (without passing on the
energy).

This propety is valid for radiation

corresponding to all wavelengths and
to all angels of incidence. Therefore,
the black body is an ideal absorber of
incident radaition.

A body's behavior with regard to

thermal radiation is characterized by 22
its transmission τ, absorption α, and
reflection ρ. For a black body, τ=0,
 BLACKBODY RADIATION
BLACKBODY RADIATION

4/27/20
Sample footer
Blackbody radiation—radiation emitted by a body
that emits (or absorbs) equally well at all
wavelengths 23
 Basic
BasicLaws
LawsofofRadiation
Radiation
Stefan Boltzmann law
All objects emit radiant energy.

4/27/20
Hotter objects emit more energy than colder objects. The amount of energy
radiated is proportional to the temperature of the object raised to the fourth
power.

 This is the Stefan Boltzmann Law

F =  T4
( F= energy flux is the rate of transfer of energy through surface)

F = flux of energy (W/m2) (W/m2 :Watts per sq. meter)

T = temperature (K)
 = 5.67 x 10-8 W/m2K4 (a constant)
The hotter the object, the shorter the wavelength () of emitted energy. 24

lmax = hc/5kT
This is Wien’s Law
 BLACK-BODY
BLACK-BODYRADIATION
RADIATIONLAWS
LAWS
2ckT
The Rayleigh-Jeans Law
The Rayleigh-Jeans Law I ( , T ) 
4

It agrees with
experimental
measurements for long

Sample footer
wave-lengths.
It predicts an energy
output that diverges
towards infinity as
wavelengths grow
smaller.
The failure has
become known as the
ultraviolet catastrophe. 25

25
 Planck’s Law of Black Body Radiation

The Planck’s Law of Black Body Radiation

states in terms of wavelength:

4/27/20
2hc 2 1
I ( , T ) 
5 hc

Sample footer
e kT  1

• The above equation related intensity

of emission with Temperature and
wavelength.
• It fits well with experimental
observation of black body radiation.

• As opposed to classical model of

continuous energy distribution, energy
is emitted in forms of quantized
packets, where h is Planck’s constant: 26

E  h  hc / 
Hotter objects emit at
shorter wavelengths.

max = 3000/T
Sun
Earth

1000 100 10 1 0.1 0.01

Hotter objects emit

 (m) more energy than
colder objects

F =  T4
 Applications of Black Body Radiation

• Roughly we can say that the stars radiate like

blackbody radiators. This is important because it
means that we can use the theory for blackbody
radiators to infer things about stars like its effective
temperature.

• Interesting applications include designing

 camouflage 
and radar absorbent materials.
 Planck-Einstein Relationship
Planck-Einstein Relationship
The wave theory of transmission of radiant energy appeared to
imply that energy was emitted (or absorbed) in continuous waves.

4/27/20
In 1900 Max Planck studied the spectral lines obtained from hot-
body radiations at different temperatures.
 According to him, light radiation was produced discontinuously by

Sample footer
the molecules of the hot body, each of which was vibrating with a
specific frequency which increased with temperature.
 Thus Planck proposed a new theory that a hot body radiates
energy not in continuous waves but in small units of waves.
The ‘unit wave’ or ‘pulse of energy’ is called Quantum (plural,
quanta). In 1905 Albert Einstein showed that light radiations
emitted by ‘excited’ atoms or molecules were also transmitted as
particles or quanta of energy. These light quanta are called
photons.

The general Quantum Theory of Electromagnetic Radiation in

its present form may be stated
29
as :
(1) When atoms or molecules absorb or emit radiant energy,
they do so in separate ‘units of waves’ called quanta or
photons. Thus light radiations obtained from energised or
‘excited atoms’ consist of a stream of photons and not continuous

4/27/20
waves.
(2) The energy, E, of a quantum or photon is given by the
relation

Sample footer
E = hν; where ν is the frequency of the emitted radiation, and h the
Planck’s Constant= = 6.626 x 10 -34 joule seconds (J s)
We know that c, the velocity of radiation, is given by the equation
c = λν
Substituting the value of ν from E =hc/λ
(3) An atom or molecule can emit (or absorb) either one
quantum of energy (hν) or any
whole number multiple of this unit.
Thus radiant energy can be emitted as hν, 2hν, 3hν, and so on, but
never as 1.5 hν, 3.27 hν,
5.9 hν, or any other fractional value of hν i.e. nhν
Quantum theory provided admirably a basis for explaining the
photoelectric effect, atomic 30
spectra and also helped in understanding the modern concepts of
atomic and molecular structure.
 Planck-Einstein Relationship
Planck-Einstein Relationship
E  h  hc / 

4/27/20
h = Planck’s Constant = 6.626 x 10 -34 joule
seconds (J s)

Sample footer
Energy could be gained or lost in individual
units or packets, with energies that are whole
number multiples of the constant, h.

31
 PLANCK’S QUANTUM THEORY
PLANCK’S QUANTUM THEORY

Radiant energy is emitted or absorbed discontinuously

4/27/20
in the form of quanta.

Sample footer
c
E  h  h  hc

  Wavelength
  Frequency
  Wave number
h  Plank ' s cons tan t
 6.626  1034 Js

32
ILLUSTRATIVE PROBLEM
The ratio of the energy of a photon of 2000 Å
wavelength radiation to that of 6000 Å wavelength
radiation is

4/27/20
(a) ¼ (b) 4

Sample footer
(b) ½ (d) 3

Solution:

hc hc hc
E  h  E1  E2 
 1 2
0
E1  2 6000 A
   0
3
E2 1 2000 A
33
Hence, answer is (d).
 Bohr’s
Bohr’smodel
modelofofan
anatom
atom
In 1913 Niels Bohr proposed a new model of atom which explained some of these
things and also the emission spectrum of hydrogen.
Bohr’s theory was based on Planck’s quantum theoryand was built on the following

4/27/20
postulates.
i) An atom has a positively charged nucleus at its centre and most of the mass of the
atom is in the nucleus.

Sample footer
ii) The electrons revolve around the nucleus in special orbits called discrete orbits.
iii) These orbits are called shells or energy levels and are represented by the letters
K, L, M, N etc. or numbered as 1, 2, 3, 4, etc.
iv) While revolving in the discrete orbits the electrons do not radiate energy.
v) An electron can move from one energy level to another by quantum or
photon jumps only.
When an electron resides in the orbit which is lowest in energy
(which is also closest to the nucleus), the electron is said to be
in the ground state.
When an electron is supplied energy, it absorbs one
quantum or photon of energy and jumps to a higher energy 34
level. The electron then has potential energy and is said to be
in an excited state. Shells or energy levels in an atom
 4/27/20
Sample footer
The quantum or photon of energy absorbed or emitted is the difference
between the lower and higher energy levels of the atom
ΔE = Ehigh – Elow = hν
where h is Planck’s constant and ν the frequency of a photon emitted or
absorbed energy.
vi) The angular momentum (mvr) of an electron orbiting around
the nucleus is an integral multiple of Planck’s constant divided
by 2π.
Angular momentum =mvr = n h/2 π
where m = mass of electron, v = velocity of the electron, r = radius of
the orbit ; n = 1, 2, 3, etc., and h = Planck’s constant.
By putting the values 1, 2, 3, etc., for n, we can have respectively the 35
angular momentum, h/2 π 2h/2 π , 3h/3 π , etc.
There can be no fractional value of h/2π. Thus the angular momentum is
 Distribution of electrons in different shells
Distribution of electrons in different shells
The distribution of electrons in the different shells was suggested by Bohr and
Bury. The following are the rules for filling electrons in the different shells.

4/27/20
i) The maximum number of electrons in a shell is given by the formula 2n2
where n is the number of the shell 1, 2, 3 etc.
First shell or K shell can have = 2n2 = 2 x 12 = 2x1x1 = 2 electrons
Second shell or L shell can have = 2n2 = 2 x 22 = 2x2x2 = 8 electrons
Third shell or M shell can have = 2n2 = 2 x 32 = 2x3x3 = 18 electrons
Fourth shell or N shell can have = 2n2 = 2 x 42 = 2x4x4 = 32 electrons
and so on.

ii) Electrons cannot be filled in a shell unless the inner shells are filled.

36
 BOHR’S POSTULATES: IN BRIEF

4/27/20
Quantization of
Retained key
angular momentum.
features of
Rutherford’s nh
mvr 
model. 2

Energy emitted/absorbed when

electrons jump from one orbit to
another. E  Ef  Ei
Concept of
stationary  h
circular orbits.
37
 SERIES OF HYDROGEN SPECTRUM (Bohr’s
Explanation)

 The solitary electron in hydrogen atom at ordinary temperature

resides in the first orbit (n = 1) and is in the lowest energy state

4/27/20
(ground state).
When energy is supplied to hydrogen gas in the discharge tube, the
electron moves to higher energy levels viz., 2, 3, 4, 5, 6, 7, etc.,

Sample footer
depending on the quantity of energy absorbed.
From these high energy levels, the electron returns by jumps to one
or
other lower energy level. In doing so the electron emits the excess
energy as a photon.
This gives an excellent explanation of the various spectral series of
hydrogen.
 Lyman series is obtained when the electron returns to the ground
state i.e., n = 1 from higher energy levels (n2 = 2, 3, 4, 5, etc.).

Similarly, Balmer, Paschen, Brackett and Pfund series are produced

when the electron returns to the second, third, fourth and fifth energy
38
levels respectively
as shown in Fig.
SERIES OF HYDROGEN SPECTRUM (Bohr’s
Explanation)

4/27/20
Sample footer
UV Visible IR IR IR
8
7
6
5 Pfund
4
Brackett
3
Paschen
2
Balmer
1 39
Lyman l
ADVANTAGES AND DISADVANTAGES OF BOHR-
ADVANTAGES AND DISADVANTAGES OF BOHR-
SOMMERFIELD MODEL
SOMMERFIELD MODEL
• Somerfield's Model predicted the splits
in the spectrum. The electrons moving on
the two orbits of the same n number but

4/27/20
of different shape have a bit different
energies which explained the splitting of
spectral lines or very closely spaced

Sample footer
spectral lines.

• Somerfield's Model also showed that

orbits don’t have to lie on the same
plane and could tilt in the presence of a
magnetic field.

• The fundamental flaw was that

orbitals could tilt relative to xy
plane only in certain discrete values.
However, observation shows that an
atom can be tilted w.r.t x,y,z co- 40
ordinates without restriction. This
flaw is to be corrected by wave
 SPECTRAL LINES IN HYDROGEN SPECTRUM
SPECTRAL LINES IN HYDROGEN SPECTRUM
No. of spectral lines in
n(n  1)
hydrogen spectrum 
2

4/27/20
n  Shell number

Sample footer
Series ni nf Region
Lyman 1 2,3,4,5… Ultraviolet
Balmer 2 3,4,5….  Visible
Paschen 3 4,5,6….  Infrared
Brackett 4 5,6,7,8…  Infrared
Pfund 5 6,7,8…..  infrared

41
 Rydberg’s Formula
ydberg’s formula is used to explain spectral
nes of hydrogen like chemical elements.

tilizing Bohr’s Postulates, it can be deduced

hat the energy of a photon emitted by a
ydrogen atom is given by the difference of two
ydrogen energy levels :
he difference in energy between the levels n1
nd n2 is given by a Redberg’s equation as:

E = En2- En1 =

s we know ΔE = hν = hc/λ

hc/λ =

where R is Rydberg constant. The value of R

1/ λ = ν = can be calculated as the value of e, m, h and c
OR are known. It comes out to be 109,679 cm– 1
and agrees closely with the value of Rydberg
1/ λ = ν = constant in the original empirical Balmer’s
equation (109,677 cm– 1).
 WAVELENGTH AND WAVE NUMBER IN TRANSITION
WAVELENGTH AND WAVE NUMBER IN TRANSITION

4/27/20
Sample footer
The Bohr model was successful in determining where all the spectral43
lines of H should be.
 Balmer Spectral Series

•The Balmer series is particularly useful

in astronomy because the Balmer lines appear
in numerous stellar objects due to the
abundance of hydrogen in the universe, and
therefore are commonly seen and relatively
strong compared to lines from other elements.

•The familiar red H-alpha spectral line of

hydrogen gas in the far right, which is the
transition from the shell n = 3 to the Balmer
series shell n = 2, is one of the conspicuous
 ILLUSTRATIVE PROBLEM
A gas sample of hydrogen atoms are shot with electrons of
12.75 eV energy.What will be the energy of radiation emitted in
Balmer series?

4/27/20
Solution Energy of an electron
in ground state  13.6 eV

Sample footer
Energy of the excited electron
 12.75  (13.6)  0.85eV
 Energy level of the electron,
13.6  Z2
 0.85  
n2 n  4

For Balmer series,n1  2, n2  4

1 1   1 1 
 energy  13.6 Z  2  2   13.6  12  2  2 
2
n 
 1 n2  2 4 
 2.55 eV
45
 Drawbacks of Bohr’s
Drawbacks of Bohr’s
Model
Model

4/27/20
Explains spectrum
of only hydrogen and
hydrogen like species
Does not explain
( single electron species) Stark effect and
Zeeman effect

No proof for
Not in accordance quantization of
with Dual nature angular momentum
and Heisenberg’s 46
uncertainty principle
 Bohr-Sommerfeld
Bohr-SommerfeldModel
Model
When spectra were examined with spectrometers, each line was found to consist
of several closely packed lines. The existence of these multiple spectral lines
could not be explained on the basis of Bohr’s theory.

4/27/20
Sommerfeld modified Bohr’s theory as follows:

Sample footer
Bohr considered electron orbits as circular but Sommerfeld postulated the
presence of elliptic orbits also. An ellipse has a major and minor axis. A circle
is a special case of an ellipse with equal major and minor axis.

The angular momentum of an electron moving in an elliptic orbit is also

supposed to be quantized. Thus only a definite set of values is permissible. It is
further assumed that the angular momentum can be an integral part of h/2π
units, where h is Planck’s constant.
Or that, angular momentum = kh/2π
where k is called the azimuthal quantum number, whereas the quantum
number used in Bohr’s theory is called the principal quantum number. The
two quantum numbers n and k are related by the expression : 47
n/k = length of major axis/length of minor axis
 Bohr-Sommerfeld
Bohr-SommerfeldModel
Model
• Bohr’s model does not
work in case of heavier
elements where the

4/27/20
spectral lines observed did
not corroborate with the

Sample footer
applied magnetic field. It
was found that spectral
lines are not homogenous Bohr’s Atomic Model
but consists of several
convenient lines.

• Sommerfield proposed
that not only do electrons
travel in certain orbits but
the orbits have different
shapes and the orbits could
tilt in the presence of a 48
magnetic field. This Bohr-Sommerfield
explained well the splitting Model
 Dual Nature
Dual Nature
(de-Broglie equation: Einstein has suggested in 1905, that light has dual character as
wave and also as particle. Louis de-Broglie proposed that electron ( or matter) also has
a dual character, as wave and as particle.

4/27/20
de Broglie Matter has both wave
According to Planck’s
and particle nature.
quantum theory
E  h (1)
According to Einstein’s equation
E  mc2 (2)
Equating (1) and (2) mc2  h de Broglie
c h wavelength
mc2  h  
 mc
h
For any particle =
mv 49
de Broglie cont………….

Replacing c by velocity (v) of electron we have

λ = h/mv = h/p

4/27/20
Where p = momentum of electron
de Broglie equation is applicable only for small particle like

Sample footer
electrons etc. and has no significance for large particle

50
HEISENBERG’S
HEISENBERG’S
HEISENBERG’S UNCERTAINTY
UNCERTAINITY
UNCERTAINTY PRINCIPLE
PRINCILE
PRINCIPLE
• It is impossible to know both the position and
momentum exactly, i.e., Dx=0 and Dp=0

• These uncertainties are inherent in the

physical world and have nothing to do with the
skill of the observer

• Because h is so small, these uncertainties are

not observable in normal everyday situations

x.p  h / 4
 ANOTHER CONSEQUENCE OF
HEISENBERG’S UNCERTAINTY PRINCIPLE

 A quantum particle can never be in a state of rest, as this

would mean we know both its position and momentum
precisely

 The more accurately we know the energy of a body, the

less accurately we know how long it possessed that
energy
HEISENBERG’S
HEISENBERG’SUNCERTAINTY
UNCERTAINTYPRINCIPLE
PRINCIPLE

The position and momentum of a subatomic particle

cannot be determined simultaneously and with absolute

4/27/20
accuracy.
h

Sample footer
x.p 
4

h
x.v  Since p=mv
4m

53
 ILLUSTRATIVE EXAMPLE
Calculate the uncertainty in position of an electron whose velocity is
3 x 104 cm s-1 accurate up to 0.001%. Mass of an electron = 9.1 x 10-
28
g.

4/27/20
Solution Heisenberg’s uncertainty principle

Sample footer
h
Þ Dx × Dp =
4
h
Dx × mDv =
4

3  104  0.001
v   0.3 cms1
100

6.626  10 27
Dx =
4  3.14  9  10 28  0.3

Dx = 1.95 cm 54
 Quantum
QuantumNumbers
Numbers
The principal quantum number n governs the

4/27/20
electron's energy and average distance from the
nucleus.

The orbital quantum number l determines the

magnitude of an atomic electron's angular
momentum.

The magnetic quantum number ml specifies the

direction of an atomic electron's angular
momentum.

The spin magnetic quantum number ms of an55

atomic electron has two possible values, +1/2 or
 Quantum
QuantumNumbers
Numbers

4/27/20
principal quantum number n 1,2,3,…..
orbital quantum number l 0,1,2,….n-1
magnetic quantum number m -l to +l
for n=2 -2,-1,0,1,2
spin magnetic quantum number +½ or –½ spin

To know where or what state the electron is in you need to

know the four quantum numbers.

56
S
Orbitals are regions in space where an electron is
likely to be found:
 90% of the time the electron is within the boundaries
described by the electron density map
 The exact path of an electron in a given orbital is not
known!

DESCRIBING ORBITALS
Use quantum numbers to describe orbitals. A given
orbital can be described by a set of 3 quantum
numbers:
1. Principal quantum number (n)
2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)

57
PRINCIPAL QUANTUM NUMBER
(N)
(n) describes the size and energy of the orbital:
 Possible values: whole number integer
1, 2, 3, …
 As “n” increases so does the size and energy of
the orbital

ANGULAR MOMENTUM QUANTUM

NUMBER (L)
(l) is related to the shape of the orbital:
 Possible values: (l) is an integer between 0 and n-1
 Each (l) value is also assigned a letter designation

58
ANGULAR MOMENTUM
QUANTUM NUMBER (L)
(l) Value Letter Designation

0 s

1 p

2 d

3 f
59
n Possible Designation
l values
1 0 1s
2 0 2s
1 2p
3 0 3s
1 3p
2 3d

4 0 4s
1 4p
2 4d
3 4f
60
 MAGNETIC QUANTUM NUMBER
(ML)
(ml) is related to the orientation of the orbital in 3-D space:
 Possible values: - l to + l

Consider the p orbital…it has an l value of 1

and thus the possible ml values are -1, 0, +1

 These 3 ml values correspond to the 3 possible

orientations of the p orbital

61
ML AND ORBITALS

l ml # orbitals

0 (s) 0 1

1 (p) -1, 0, 1 3

2 (d) -2, -1, 0, 1, 2 5

3 (f) -3, -2, -1, 0, 1, 2, 3 7

62
QUANTUM NUMBER SUMMARY
 A set of 3 quantum numbers describes a specific orbital
 Energy and size - n
 Shape - l

 Orientation – m
l

4TH QUANTUM NUMBER!

A 4th quantum number was added to describe the
spin on a given electron.
 Called the electron spin quantum number - ms
 Possible values: +1/2 and -1/2

63
 STERN-GERLACH EXPERIMENT

The Stern–Gerlach experiment involves sending a beam of particles

through an inhomogeneous magnetic field and observing their deflection.
The results show that particles possess an intrinsic angular momentum that
is most closely analogous to the angular momentum of a classically
spinning object, but that takes only certain quantized values (ie is not
continuous).
THE S-ORBITAL
THE S-ORBITAL

4/27/20
Sample footer
65
P-ORBITALS
P-ORBITALS

4/27/20
66
4/27/20 Sample footer
67

The d orbitals
4/27/20 Sample footer
68

The f orbitals
 AUFBAU
AUFBAUPRINCIPLE
PRINCIPLE
In German, "Aufbau" means "construction" (also Aufbau rule

4/27/20
or building-up principle), is used to determine the electron
configuration of an atom, molecule or ion.

Sample footer
The principle postulates a hypothetical process in which an
atom is "built up" by progressively adding electrons

According to the principle, electrons fill orbitals starting at the

lowest available (possible) energy states before filling higher
states (e.g. 1s before 2s).

The order in which these orbitals are filled is given by the n+
rule, where orbitals with a lower n+ value are filled before
those with higher n+ values.

For the same n+ value, those with lower n values will be filled
first.
69
 Principles and rules to write the
Principles and rules to write the
electronic configuration
electronic configuration

4/27/20
1. Aufbau principle

Sample footer
2. Pauli’s exclusion principle

3. Hund’s rule of maximum multiplicity

70
Order for Filling Atomic Subshells
Order for Filling Atomic Subshells
n+ 
=1 n+  =2
n+  =3

4/27/20
n+  =4

71

71
Order
Orderfor
forFilling
FillingAtomic
AtomicSubshells
Subshells

4/27/20
Sample footer
72
PAULI’S
PAULI’SEXCLUSION
EXCLUSIONPRINCIPLE
PRINCIPLE

In an atom no two electrons can have the

4/27/20
same set of four quantum numbers.

Sample footer
different
73
 The Pauli Exclusion Principle
 The maximum number of electrons and their
orbital diagrams are:

4/27/20
No. Values Max No.
Sub
Electron
Shell Orbitals (-l to +l)

Sample footer
s

s (l = 0) 1 (0) 2

p (l = 1) 3 (-1, 0, +1) 6

d (l =2) 5 (-2,-1,0,+1,+2) 10

7 (-3,-
f (l =3) 14
2,1,0,+1,+2,+3)

74

04/27/202 74
 HUND’S RULE OF MAXIMUM MULTIPLICITY
HUND’S RULE OF MAXIMUM MULTIPLICITY

Among the orbitals of same energy, electrons do not start pairing, until
all these orbitals are singly occupied”.

4/27/20
Hund’s rule is also called as the principle of minimum pairing and the
principle of maximum multiplicity.

Case - 1 1s2 2s2 2px1 2py1 2pz1

2px2 2py1 2pz1

Case - 2 1s 2s2
2

75
GROUND STATE ELECTRON CONFIGURATION OF ELEMENT
GROUND STATE ELECTRON CONFIGURATION OF ELEMENT

Each electron shell can hold a maximum of 2n2 electrons

where n is the shell number

4/27/20
These electrons are accommodated in s, p, d and f orbitals,
the maximum number of electrons in each type of orbitals

Sample footer
being determined by its electron-holding capacity (for s = 2,
p = 6, d = 10 and f = 14)

In the ground state of an atom, the electrons tend to occupy

the available orbitals in the increasing order of energies,
the orbitals of lower energy being filled first

Any orbital may have one or two electrons at the most

When several orbitals of equal energy (degenerate orbitals)

are available, electrons prefer to occupy separate orbitals
rather than getting paired in the same orbital
76
 SCHRODINGER WAVE EQUATION

Describes the probability of finding an

4/27/20
electron in a given volume element.

Sample footer
2  2  2 8  2m
   (E  V)   0
2 2 2 2
x y z h

2  Probability of finding the electron in a given region.

  Describes the wave motion of the electron.

hrodinger’s equation can only be solved exactly for the hydrogen atom.
pproximations have to be made to solve it for multi-electron systems.
77
 The Schrodinger Equation

4/27/20
Sample footer
Solving this equation will give us
• the possible energy levels of a system (such as an atom)
• The probability of finding a particle in a particular region of
space

It’s hard to solve this equation. Therefore, our approach will be to

learn about a few of the simpler situations and their solutions.
78
PARTICLE IN A BOX

4/27/20
Sample footer
Rigid walls Potential energy
Newton’s view function U(x)

79
 THE PARTICLE IN A BOX IS NOT FREE,
IT IS “BOUND” BY U(X)

4/27/20
Examples: An electron in a long molecule or in a straight wire

Sample footer
To be a solution of the SE,
(x) has to be continuous
everywhere, except where
U(x) has an infinite
discontinuity

“Boundary conditions”:
(x) = 0 at x=0, L and all values of x outside 80
this box, where U(x) = infinite
 SOLUTIONS TO THE S.E. FOR THE
PARTICLE IN A BOX

4/27/20
d/dx also has to be
continuous everywhere,

Sample footer
(except where U(x) has an
infinite discontinuity)
because you need to find
d2/dx2

Normal modes of a vibrating string! 81

 4/27/20
Sample footer
From 0 < x < L, U(x) = 0, so in this
region, (x) must satisfy:

 d 2 2
 2
 E (x)
2m dx
Same as a free particle?!?!?!?!?
82
 You may be tempted to conclude that

 (x)  Ae ikx
, the solution for a free particle, is a

4/27/20
possible solution for the bound one
too.

Sample footer
WRONG!!!!
Why not?
The above (x) does NOT satisfy the boundary conditions
that (x) = 0 at x=0 and x=L.

83
SO WHAT IS THE SOLUTION THEN?

4/27/20
Try the next simplest solution, a superposition of two
waves

Sample footer
 (x)  A1e  A2e ikx ikx

2 2
k
The energy again is E
 2m
84
WAVE FUNCTIONS FOR THE
PARTICLE IN A BOX
(x) = 0

4/27/20
Sample footer
85
THE ENERGY OF A PARTICLE IN A BOX
CANNOT BE ZERO!

4/27/20
Sample footer
You could try to put n = 0 into this equation, but
then (x) = 0, which would mean there is no
particle!

86
The function (x) = C sin(kx)is a solution to the Schrodinger Eq. for
the particle in a box

Probability distribution function

Wave function

87
INFINITE SQUARE-WELL POTENTIAL
 The simplest such system is that of a particle trapped in a box
with infinitely hard walls that the particle cannot penetrate. This
potential is called an infinite square well and is given by

 Clearly the wave function must be zero where the potential is

infinite.

 Where the potential is zero inside the box, the Schrödinger

wave

equation becomes where .

 The general solution is .

88
N

 Boundary conditions of the potential dictate that the wave

function must be zero at x = 0 and x = L. This yields valid
solutions for integer values of n such that kL = nπ.

 The wave function is now

 We normalize the wave function

 The normalized wave function becomes

 These functions are identical to those obtained for a vibrating

89
string with fixed ends.
QUANTIZED
ENERGY
 The quantized wave number now becomes
 Solving for the energy yields

 Note that the energy depends on the integer values of n.

Hence the energy is quantized and nonzero.
 The special case of n = 0 is called the ground state energy.

90
SIMPLE HARMONIC
OSCILLATOR
 Simple harmonic oscillators describe many physical situations: springs,
diatomic molecules and atomic lattices.

 Consider the Taylor expansion of a potential function:

Redefining the minimum potential and the zero potential, we have

Substituting this into the wave equation:

91
Let and which yields .
PARABOLIC POTENTIAL
WELL

 If the lowest energy level is zero, this violates the uncertainty principle.
 The wave function solutions are where Hn(x) are Hermite
polynomials of order n.

 In contrast to the particle in a box, where the oscillatory wave function is

a sinusoidal curve, in this case the oscillatory behavior is due to the
polynomial, which dominates at small x. The exponential tail is provided
by the Gaussian function, which dominates at large x. 92
ANALYSIS OF THE PARABOLIC POTENTIAL WELL

 The energy levels are given by

 The zero point energy is called the Heisenberg

limit:

 Classically, the probability of finding the mass

is greatest at the ends of motion and smallest
at the center (that is, proportional to the
amount of time the mass spends at each
position).
 Contrary to the classical one, the largest
probability for this lowest energy state is 93
for
the particle to be at the center.
A diatomic molecule vibrates somewhat like two masses on a spring
with a potential energy that depends upon the square of the
displacement from equilibrium. But the energy levels are quantized
at equally spaced values.
The energy levels of the quantum harmonic oscillator are and for a
diatomic molecule the natural frequency is of the form

mm
where the reduced mass is given
m  by1 2

m1  m2

This form of the frequency is the same as that for the classical
simple harmonic oscillator. The most surprising difference for the
quantum case is the so-called zero-point vibration" of the n=0
ground state. This implies that molecules are not completely at rest,
even at absolute zero temperature.
The quantum harmonic oscillator has implications far beyond the
simple diatomic molecule. It is the foundation for the understanding
of complex modes of vibration in larger molecules, the motion of
atoms in a solid lattice, the theory of heat capacity, etc. In real
systems, energy spacings are equal only for the lowest levels where
94
the potential is a good approximation of the "mass on a spring" type
harmonic potential. The anharmonic terms which appear in the
potential for a diatomic molecule are useful for mapping the