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General Information
• Lecturer: Assoc. Prof., Dr. Trần Vĩnh Hoàng
• Email:baigiang.hvt.sce@gmail.com /
hoang.tranvinh@hust.edu.vn
• School of Chemical Engineering
Department of Inorganic Chemistry Part I- Fundamentals of chemical compositions
• Office: C1- 408
• Tel: 024.38680110 Chapter 1
• Department’s Laboratories: C1-(405; 406; 416 and 403)

Textbook:
Electronic Structure of Atoms

Dalton’s Atomic Theory (1808)

1 Chapter 1: Compositions of atoms and periodic table
1.1. Components of the atom
1.2. The atomic theory of Boh’rs
1.3. The principles of quantum mechanics 1. Elements are composed of extremely small particles
1.3.1. The wave nature of the electron called atoms.
1.3.2. The uncertainty principle
1.3.3. The quantum mechanical picture of the atom 2. All atoms of a given element are identical, having the
1.3.3.1. Wave function same size, mass and chemical properties. The atoms of
1.3.3.2. Schrodinger wave equation one element are different from the atoms of all other
1.4. The solution of the Schrodinger equation for one electron species elements.
1.4.1. Quantum numbers
1.4.2. Atomic orbitals 3. Compounds are composed of atoms of more than one
1.5. Electron configurations: element. In any compound, the ratio of the numbers of
1.5.1. The shielding effect in many- electron atoms atoms of any two of the elements present is either an
1.5.2. The general rules for arranging electrons to atomic orbitals
integer or a simple fraction.
1.6. Period ‘s law and periodic table
1.6.1. The periodic table and electron structure of atoms in periodic table 4. A chemical reaction involves only the separation,
1.6.2. Periodic variation in physical properties combination, or rearrangement of atoms; it does not
1.7. Coordination compounds result in their creation or destruction.
3 4

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Millikan’s Experiment

Measured mass of e-
(1923 Nobel Prize in Physics)

e- charge = -1.60 x 10-19 C

Thomson’s charge/mass of e- = -1.76 x 108 C/g
mass p ≈ mass n ≈ 1840 x mass e-
e- mass = 9.10 x 10-28 g 5 6

Atomic number, Mass number and Isotopes

Atomic number (Z) = number of protons in nucleus
Mass number (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
Isotopes are atoms of the same element (X) with different
numbers of neutrons in their nuclei

Mass Number A
ZX
Element Symbol
Atomic Number

1 2 3
1H 1H (D) 1H (T)
235 238
92 U 92 U 7 8

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Line Emission Spectrum of Hydrogen Atoms

9 10

Bohr’s Model of
the Atom (1913)
Ephoton = DE = Ef - Ei
1. e- can only have specific
ni = 3 ni = 3 1
(quantized) energy Niels Henrik David Bohr
Ef = -RH ( )
values (1885-1962, Denmark) n2f
Nobel Prize in Physics in 1922
2. light is emitted as e- ni = 2 1
Ei = -RH ( 2 )
moves from one energy nf = 2 ni
level to a lower energy 1 1
level DE = RH( 2 )
1 ni n2f
En = -RH ( )
n2

n (principal quantum number) = 1,2,3,… nnf f==11

RH (Rydberg constant) = 2.18 x 10-18J
11 12

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Calculate the wavelength (in nm) of a photon emitted

by a hydrogen atom when its electron drops from the
n = 5 state to the n = 3 state.

1 1
Ephoton = DE = RH( )
n2i n2f
Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)
Ephoton = DE = -1.55 x 10-19 J
Ephoton = h x c / l
l = h x c / Ephoton
l = 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
l = 1280 nm
13 14

De Broglie
(France, 1892 – 1987)
Nobel Prize for Physics in 1929

De Broglie (1924) reasoned that

e- is both particle and wave.
h v = velocity of e-
l = mv
m = mass of e-

Though this seems like a very short wavelength, it is

similar to the spacing between atoms in many
crystals. A stream of such electrons hitting a crystal
15 gives measurable diffraction patterns. 16

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 The German physicist Werner Heisenberg proposed that

the dual nature of matter places a fundamental limitation on
how precisely we can know both the location and the
momentum of an object at a given instant.
 The limitation becomes important only when we deal with
matter at the subatomic level (that is, with masses as small
as that of an electron).
 Heisenberg’s principle is called the uncertainty principle.
When applied to the electrons in an atom, this principle
Werner Heisenberg
states that it is impossible for us to know simultaneously
(1901–1976). During his both the exact momentum of an electron and its exact
postdoctoral assistantship with
location in space.
This wavelength is far too short to give any measurable Niels Bohr, Heisenberg
formulated his famous uncertainty
effects. Recall that atomic diameters are in the order of 10 m, 10
principle. At 32 he was one of the
youngest scientists to receive a
which is 24 powers of 10 greater than the baseball Nobel Prize (1932).

“wavelength.”
Where: Δx -the uncertainty in position,
Δ(mv) -the uncertainty in momentum,
h- the Planck constant:

17 18

Where 90% of the

e- density is found
for the 1s orbital

Electron-density distribution. This rendering represents

the probability, 2, of finding the electron in a hydrogen
atom in its ground state. The origin of the coordinate
19 20
system is at the nucleus.

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Schrodinger Wave Equation

Erwin Rudolf Josef Alexander Schrödinger
In 1926 Schrodinger wrote an equation that (1887-1961) (Austria-Hungary) Nobel Prize
in Physics (1933)
described both the particle and wave nature of the e-
Wave function () describes:
1. energy of e- with a given 
2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.

21 22

1. Principal quantum number n

Schrodinger Wave Equation
n = 1, 2, 3, 4, ….
 is a function of four numbers called
quantum numbers (n, l, ml, ms) i-Main energy level of atomic orbital (AO)
me4 Z2 Z2
Where: n-principal quantum number; En   Z 2  2,18.1018 2 J  13.6 2 eV
l -angular momentum quantum number, 8 0 n h
2 2 2
n n
ml- magnetic quantum number, ii-Distance of e- from the nucleus (size of AO)
ms-spin quantum number,

n=1 n=2 n=3

23 24

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2. The angular momentum quantum number l

i –The angular momentum quantum number l
 The angular momentum quantum number, l, designates the designates the SHAPE and NAME of the AO
shape of the region in space that an electron occupies.
 Within a shell (defined by the value of n, the principal quantum NAME of the AO
number) different sublevels or subshells are possible, each
with a characteristic shape.
 The angular momentum quantum number designates a
sublevel, or specific SHAPE and NAME of atomic orbital that l=0 s orbital
an electron may occupy. n = 1, l = 0 l=1 p orbital
 The angular momentum quantum number is depended to the n = 2, l = 0 or 1 l=2 d orbital
Principal quantum number n. Therefore, this number ,l, may
n = 3, l = 0, 1, or 2 l=3 f orbital
take integral values from 0 up to and including (n - 1)

for a given value of n, l = 0, 1, 2, 3, … n-1

25 26

SHAPE of the AO
l=0 s orbital

l = 0 (s orbitals)

28

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SHAPE of the AO
l=1 p orbital
l = 1 (p orbitals)

2p

3p

4p 30

SHAPE of the AO
l=3 f orbital
l = 2 (d orbitals)

31

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ii- The angular momentum quantum number l

designates a Sub-energy level of the AO in one
layer of AOs

E2s < E2p

E3s < E3p < E3d

33 34

3-The magnetic quantum number ml for a given value of l

 The magnetic quantum number, m, designates the specific ml = -l, …., 0, …. +l
orbital within a subshell.
orientation of the orbital in space
 AO within a given subshell differ in their orientations in
space, but not in their energies.
 Within each subshell, m may take any integral values from -l
through zero up to +l and including :
if l = 1 (p orbital), ml = -1, 0, or 1 3

for a given value of l

ml = -l, …., 0, …. +l
orientation of the orbital in space

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2
35 36

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for a given value of l if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

ml = -l, …., 0, …. +l 5 orientations is space
if l = 1 (p orbital), ml = -1, 0, or 1 3 orientations is space

5 orientations is space
3 orientations is space
m= -1 m=0 m= +1 m= -2 m= -1 m=0 m= +1 m= +2

p orbital 37 d orbital 38

4. The spin quantum number ms Schrodinger Wave Equation

 The spin quantum number, m , refers to the spin of
s

an electron and the orientation of the magnetic field

produced by this spin. (n, l, ml, ms)
 For every set of n, l, and ml values, ms can take the
value or spin quantum number ms
ms = +½ or -½

ms = +½ ms = -½

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Schrodinger Wave Equation

quantum numbers: (n, l, ml, ms)
Existence (and energy) of electron in atom is described
by its unique wave function .
Pauli exclusion principle - no two electrons in an atom
can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8)

Each seat can hold only one individual at a
time

41 42

Schrodinger Wave Equation How many 2p orbitals are there in an atom?

quantum numbers: (n, l, ml, ms) n=2
If l = 1, then ml = -1, 0, or +1
Shell – electrons with the same value of n 2p
3 orbitals
l=1
Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

How many electrons can be placed in the 3d subshell?
How many electrons can an orbital hold?
n=3 If l = 2, then ml = -2, -1, 0, +1, or +2
If n, l, and ml are fixed, then ms = ½ or - ½
3d 5 orbitals which can hold a total of 10 e-
 = (n, l, ml, ½) or  = (n, l, ml, -½)
An orbital can hold 2 electrons
43 l=2 44

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Energy of orbitals in a single electron atom

Energy only depends on principal quantum number n

4px + 4py + 4pz =3 AO

n=3
1s =1 AO
n=2
4dx2-y2 =1 AO
1
En = -RH ( )
Is not an AO (l = n = 3) n2

n
3dxy+3dzy+3dxz+3dx2-y2+ 3dz2=5 AO n=1
l 20/02/2021
m??? 45 46

Energy of orbitals in a multi-electron atom

Electron configuration is how the electrons are
Energy depends on n and l distributed among the various atomic orbitals in an
atom.
number of electrons
in the orbital or subshell
n=3 l = 2 1s1
n=3 l = 1
principal quantum angular momentum
n=3 l = 0 number n quantum number l

n=2 l = 1
n=2 l = 0
Orbital diagram

H
n=1 l = 0 1s1
47 48

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The electronic structures of atoms are

1.5. ELECTRON CONFIGURATIONS
 The electron cloud of an atom is assumed to be the
superposition of charge clouds, or orbitals, arising from
the individual electrons; these orbitals resemble the
atomic orbitals of hydrogen.
 The electronic arrangement that we will describe for
each atom is called the ground state electron
configuration. This corresponds to the isolated atom in
its lowest energy, or unexcited, state.
 Following three rule as below
a. Pauli Exclusion Principle
b. Klechkowsky rule
c. Hund’s rule
 After electrons was distributed into AO. All the filled AOs
49
should be re-organized by shell (n) and by sub-shell
governed by the Pauli Exclusion Principle
The Pauli exclusion principle states that no
two electrons in an atom can have the same Wolfgang Ernst Pauli
set of four quantum numbers n, l, ml, and ms.
(1900-1958) (Austria-Hungary,
Switzerland, United States)
Nobel Prize in Physics (1945)
 For a given orbital, the values of n, l, and ml are fixed. Thus, if we want
to put more than one electron in an orbital and satisfy the Pauli
exclusion principle, our only choice is to assign different ms values to
the electrons. Because there are only two such values, we conclude
that an orbital can hold a maximum of two electrons and they must have
opposite spins.
 This restriction allows us to index the electrons in an atom, giving their
quantum numbers and thereby defining the region in space where each
electron is most likely to be found. It also provides the key to
understanding the remarkable structure of the periodic table of the
50
elements.

 For a given orbital, the values of n, l, and ml are fixed. Thus, if we

 This restriction allows us to index the electrons in an atom, giving
want to put more than one electron in an orbital and satisfy the Pauli
their quantum numbers and thereby defining the region in space
exclusion principle, our only choice is to assign different ms values to
where each electron is most likely to be found. It also provides the
the electrons. Because there are only two such values, we conclude
key to understanding the remarkable structure of the periodic table of
that an orbital can hold a maximum of two electrons and they must
the elements.
have opposite spins.
n = 1, l = 0, ml = 0, ms= +1/2 Sub-shell name s p d f
He 1s2 Number of AO in a Sub-shell) 1 3 5 7
n = 1, l = 0, ml = 0, ms= -1/2
Total number of electrons in each sub-shell 2 6 10 14

n = 1, l = 0, ml = 0, ms= +1/2 Shell n 1 2 3 4 5 6 7

n = 1, l = 0, ml = 0, ms= +1/2 Number of sub-shell in each shell n 1 2 3 4 5 6 7

Number of atomic orbitals (AO) in 1 4 9 16 25 36 49

n = 1, l = 0, ml = 0, ms= -1/2 each shell n is n2
Total number of electrons in each 2 8 18 32 50 72 98
n = 1, l = 0, ml = 0, ms= -1/2
shell n (is eq. 2n2)
51 52

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b. Klechkowsky rule
Sub-shell: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d
(n + l) value 1 2 3 3 4 4 5 5 5 6 6 6 7 7 7 7 8 8

The subshell ordering by this rule is 1s, 2s, 2p, 3s, 3p, 4s,
In neutral atoms, the approximate order in which subshells are 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, 8s, 5g, ...
filled is given by the n + ℓ rule, also known as the:
•Madelung rule
•Janet rule Order of orbitals
•Klechkowsky rule (filling) in multi-
•Wiswesser's rule
•Aufbau approximation
electron atom
•Uncle Wiggly path or
•diagonal rule

53
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
54

“Fill up” electrons in lowest energy orbitals (Aufbau principle)  Exceptions to the Klechkowsky rule
 When we fill the 3d set of orbitals, from 21Sc to 30Zn, we see
that these orbitals are not filled quite regularly. As the 3d
orbitals are filled, their energies get closer to that of the 4s
orbital and eventually become lower.
 If the order of filling of electrons on chromium (24Cr)
?? gave the expected configuration, it would be: [Ar] 4s23d4.
Chemical and pectroscopic evidence indicates, however,
Li
Be
B5
C 6
34electrons
electrons that the configuration of Cr has only one electron in the
BBe 22s
Li1s1s
1s 222s
22p
2s 12 1 4s orbital, [Ar] 4s13d5. For this element, the 4s and 3d
orbitals are nearly equal in energy.

H
He12electron
electrons  Six electrons in these six orbitals of nearly the same energy
are more stable with the electrons all unpaired:
He 1s12
H 1s [Ar] 3d
rather than the predicted order:
55
[Ar] 3d 56

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 Exceptions to the Klechkowsky rule  Exceptions to the Klechkowsky rule

With the elements d, you will find a number of exceptions to
the electron configurations predicted from the Aufbau Principle.
You should realize that statements such as the Aufbau
Principle and the (n +1) rule merely represent general
guidelines and should not be viewed as hard-and-fast rules;
the total energy of the atom is as low as possible.
(n – 1)d4ns2  (n – 1)d5ns1
(n – 1)d9ns2  (n – 1)d10ns1
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Some of the reasons for exceptions are
1. The Aufbau order of orbital energies is based on calculations
for the hydrogen atom, which contains only one electron. The
orbital energies also depend on additional factors such as the
nuclear charge and interactions of electrons in different
occupied orbitals.
2. The energy scale varies with the atomic number.
3. Some orbitals are very close together, so their order can
change, depending on the occupancies of other orbitals.
Some types of exceptions to the Aufbau order are general
enough to remember easily, for example, those based on the
special stability of filled or half-filled sets of orbitals.
4. Other exceptions are quite unpredictable. Your instructor
may expect you to remember some of the exceptions.
58

c. Hund’s rule

The most stable arrangement of electrons in subshells is the

one with the greatest number of parallel spins .

C 97
N
O
F
Ne 6810
electrons
electrons
electrons
Ne
C
N
O 1s222s
F 1s 22s222p
22p5
246
3 Paramagnetic Diamagnetic
unpaired electrons all electrons paired

59
2p 2p 60

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Paramagnetism and Diamagnetism
Substances that contain unpaired electrons are weakly attracted
into magnetic fields and are said to be paramagnetic. By contrast,
those in which all electrons are paired are very weakly repelled by
magnetic fields and are called diamagnetic.
The magnetic effect can be measured by hanging a test tube full of
a substance on a balance by a long thread and suspending it
above the gap of an electromagnet
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 When the current is switched on, a paramagnetic substance
such as copper(II) sulfate is pulled into the strong field. The
paramagnetic attraction per mole of substance can be
measured by weighing the sample before and after
energizing the magnet. The paramagnetism per mole
increases with increasing number of unpaired electrons per
formula unit.
 Many transition metals and ions have one or more unpaired
electrons and are paramagnetic. The metals of the iron triad
(Fe, Co, and Ni) are the only free elements that exhibit
ferromagnetism.
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