Atomic Structure & Interatomic

Bonding
ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

• Why are metals ductile while ceramics are brittle?

• Why do metals have reflective surfaces?

• Why most of the ceramics are insulators?

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• What is the significance of bond angle?
 Why Atomic Structure is Important?

Some properties of solid materials depend on atomic

nature and its arrangement

Ø Type of bonding (interactions among the

atoms)
determines many properties, i.e Tm, α, E, etc.

Ø Type of atomic arrangements

crytalline or amorphous

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 Why Atomic Structure is Important?

GRAPHITE DIAMOND

Graphite: Soft and greasy feel different type of interatomic bonding in

Diamond: Hardest material graphite and diamond.
known

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 Atomic Structure
Atom = nucleus (protons & neutrons) and electrons

Electrons are negatively (-) charged

Charge of an electron = - 1.6 x 10-19 C

Protons are positively (+) charged

Charge of a proton = +1.6 x 10-19 C

Neutrons are electrically neutral “particles” 4

 Atomic Structure
q Atomic Number (Z):
#protons (per atoms)
àchemical identification of element

q Mass Number (A):

#protons + #neutrons

In an electrically neutral atom: # protons = #electrons

Atomic Weight: Weighted average of the atomic masses of the atom’s naturally
occuring isotopes.

Example: 12C, 13C, 14C

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 Atomic Structure

Atomic mass unit (amu):

1 amu = 1/12 of mass of Carbon 12 (isotope of
C)
Ø The atomic mass of 12C atom is 12 amu

Mole:
Amount of matter with mass in grams equal to
the atomic mass in amu.
Ø A mole of carbon has a mass of 12 grams.
Ø 1 mole contains Avogadro’s number
(Nav = 6.022 × 1023) of atoms or molecules.

1 amu/atom (or molecule) = 1 g/mol

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 Structure of Atom
1) Bohr Atomic Model
2) Wave-Mechanical Model

q BOHR ATOMIC MODEL:

(Used hydrogen atom)

1) Electrons are assumed to be positioned around the nucleus in discrete orbitals

2) Position of the electron is more or less well defined in its orbital.

Nucleus: Z = # protons
N = # neutrons 7
Energy of Electrons
q Bohr Atomic model describe the electrons in terms of their positions
(orbitals) and energy (quantized energy levels by Rydberg equation).

E= - (2π2me4/n2h2) = - (13.6/n2) eV Energy of hydrogen

electron states
e: electron charge
m: electron mass
n: principal quantum number or principal energy levels(1,2,3,….)
h:Planck’s constant

An electron can change its energy level

To a higher level by absorbing energy, to a lower level by emitting
energy

Example: 1 eV = 1.602 x 10-19 J

n=1 Þ E1 = -13.6 eV
n=2 Þ E2 = - 3.4 eV E2>E1

If electron changes its energy level from 1 to 2 (from lower to higher energy level)
It must absorb energy, and the amount of energy absorbed;
DE =E2 - E1 = -3.4 – (-13.6) = 10.2 eV
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Allowed energy levels for hydrogen electron in Bohr Model

Ionization energy:
Energy required to remove the electron completely from the atom

Ionization energy for hydrogen electron is 13,6 eV

Figure.The first three electron energy states for the Bohr hydrogen aton

* Bohr’s model was not able to explain quantitatively the spectra of the atoms more complex
than hydrogen and the model could not have been modified.
Solution is found by
Wave-Mechanical Model 9
 Problem???
1) Bohr Atomic Model
2) Wave-Mechanical Model

q BOHR ATOMIC MODEL:

(Used hydrogen atom)

1) Electrons are assumed to be positioned around the nucleus in discrete orbitals

2) Position of the electron is more or less well defined in its orbital.

Nucleus: Z = # protons
N = # neutrons 10
Wave-Mechanical Model

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 q WAVE-MECHANICAL MODEL:

q Limitations of Bohr model was resolved by this model and electrons are
considered to behave both wave-like and particle-like. (Erwin Schrodinger)
q Electrons are no longer treated as a particle moving in discrite orbitals.

Position of electron is described by a probability distribution or electron cloud

Heisenberg’s uncertainty principle;

Position and momentum of a small particle such as
an electron can not be determined simultaneously.

BOHR MODEL WAVE-MECHANICAL

MODEL

Since the position of an electron can not be precisely determined,

an electron charge cloud density distribution is used

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Motion of electron around its nucleus and its energy is
characterized by 4 QUANTUM NUMBERS (n, l, ml, ms)
The size, shape, and spatial orientation of an electron’s probability density are
specified by these numbers.
1) Principal Quantum Number (n): Integers!!! Position, distance…
(n =1-7)
n=1 (1.shell, K) n= 2. shell (L), …

Integers? 13
 Motion of electron around its nucleus and its energy is
characterized by 4 QUANTUM NUMBERS (n, l, ml, ms)

2) Secondary quantum number, l:

Specifies subenergy levels within the main energy levels(subshells)
and related to shape of the electron subshell

l=0..n-1
Number designation of l: 0 1 2 3 4 5....
Letter designation of l : s p d f g h

Principle quantum
number, n
Shell Designation Subshells
Orbital Shapes
1 K s

2 L s,p

3 M s,p,d

4 N s,p,d,f

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 3) Magnetic quantum number, ml:
Number of orbitals or energy states for each subshell
ml=2l+1
Example: For a given l, ml can range from +l to –l
l=0 (s subshell) Þ ml = 1 energy state (0)
l=1 (p subshell) Þ ml = 3 energy states (+1, 0, -1)
l=2 (d subshell) Þ ml = 5 energy states (+2,+1, 0, -1,-2)

Pauli’s Exclusion Principle:

No two electrons can have the identical values for all four of their quantum numbers

4) Electron spin quantum number, ms:

Specifies two allowed spin directions for an electron.
ms = +1/2 and -1/2

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Orbitals
Orbital Shapes Electron density in s and p- orbitals

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Comparison of electron energy states in
Bohr and Wave-mechanical Models

BOHR MODEL WAVE-MECHANICAL MODEL

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The maximum number of electrons in each shell in an atom is 2n2

***Electrons fill up the lowest

possible energy states in the 18
electron shells and subshells
 Electron Configurations
q Represents the manner in which the states are occupied

q The number of electrons in each subshell is indicated by a superscript

after the shell-subshell designation.

Example:
H 1s1
He 1s2
Na 1s22s22p63s1

Na 1s22s22p63s1
p subshell has three orbitals:
ml=-1,0,+1, each of these orbitals
Principal quantum number,n contains 2 electrons
(SHELL K,L,M,..)

Secondary quantum number,l s subshell has one orbital: ml=0

Orbital contains 2 electrons
(SUBSHELL; s,p,d,f) 19
Valance Electrons:The electrons occupying the outermost shell
These electrons participate in bonding. Many of the physical and chemical
properties of solids are based on these valence electrons.

Stable electron configurations

• have complete s and p subshells
• tend to be unreactive. (inert, or noble, gases)

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 Survey of Elements
* Most of the elements are not stable.
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1
1s22s22p2
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d10 4s246 (stable)

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 Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions. 22
 Periodic Table-Electronegativity
Electronegativity increases from left to right

Electronegativity è how willing atoms are to accept electrons.

è the degree to which an atom attracts electrons to itself.

Ranges from 0.7 to 4.0

(large values: tendency to acquire electrons)

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Metals are electropositive – can give up their few valence electrons to become positively charged ions
Atomic Bonding in Solids
Fnet = FAttractive + FRepulsive

dE
E = - ò Fdr, F = -
dr
the centers of two atoms will
remain separately by r0

Net force is zero (equilibrium state)

r0=equilibrium spacing

• E0 (Bond energy): Energy required

to seperate these two atoms to an
infinite seperation
• Physical properties are related to
interatomic forces that bind the
atoms together

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Enet = EAttractive + ERepulsive
 Atomic Bonding in Solids
Bonding Energy

repulsion
Potential Energy, E

Too close

Atomic bonding can be explained by

interaction of two isolated atoms

0 Interatomic distance, r

attraction

equilibrium Too far

Enet = EAttractive + ERepulsive

Atoms in the bonded state
are more stable than they Optimal distance,
are unbounded most stable state 25
 Properties From Bonding: Tm

• Bond length, r • Melting Temperature, Tm

Energy
r

• Bond energy, Eo r
o r
Energy

unstretched length
r
o r
Eo

“bond energy”

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 Properties From Bonding: E
Initial length
L0 • Elastic modulus, E
Cross
sectional Energy
undeformed area A0
DL
unstretched length
deformed F r Stretched r
o
r
Elastic modulus

F DL Energies
=E
Ao Lo required
to stretch
F

E E ~ curvature at ro
~ bond energy
DL
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 Properties From Bonding: α
• Coefficient of thermal expansion, α
length, L o coeff. thermal expansion
unheated, T 1
ΔL ΔL
Lo
= α (T2 -T1 )
heated, T 2

• α ~ symmetric at ro

Energy

unstretched length
r
o
r

Eo
Eo 28
 Types of Bondings

1)Primary Bonding:
Ø Ionic bonding
Ø Covalent bonding
Ø Metallic bonding

2)Secondary bonding:
Ø Fluctuating Induced Dipole
Ø Polar Molecule-Induced Dipole
Ø Permanent Dipole Bonds
 Ionic Bonding
• Occurs between + and – ions, oppositely charged ions

• Requires electron transfer.

• Large difference in electronegativity required.

• The ionic bonding is non-directional, that is the magnitude of the bond

is equal in all directions.

• Lattice structures.

• The predominant bonding in ceramics is ionic.

Examples: AgCl, MgI2, MgO, Al2O3, etc...

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 Ionic Bonding

Ionic bond – metal + nonmetal

donates/gives accepts
electrons electrons

Eg: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

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 Ionic Bonding
Eg: NaCl
11 Protons Na 1S2 2S2 2P6 3S1 donates 1e-
11 Protons Na+ 1S2 2S2 2P6 10 e- left

17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives 1e-

17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-

•Electron transfer reduces energy of the

system

•Na shrinks and Cl expands due to an

increase in electron-proton ratio

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 Ionic Bonding

NaCl
MgO
CaF2
CsCl

Give up electrons Acquire electrons

The larger the difference in electronegativity between two atoms, the more ionic the bond.
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 Covalent Bonding
• Found in compounds made of only nonmetals.

• Sharing of valence electrons between adjacent atoms.

Ø to get a filled valence shell

• Electronegativities are comparable, similar electronegativity.

• Covalent bonding is highly-directional.

• Molecules.

• Covalent bonds may be extremely strong (like in diamonds) or may be

weak (like in Bismuth). Polymeric materials are covalently bonded
materials.

Examples: Cl2, F2, CH4, H2O, CO2, HNO3, HCl, HF, GaAs, SiC, etc...
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 Covalent Bonding
• Eg: H2 molecule
ZH =1 (1S1)
N’ = 1, 2 - N’ = 1 ® can form only one covalent bond

Each H: has 1 valence e-,

needs 1 more

• Eg: Cl2 molecule

ZCl =17 (1S2 2S2 2P6 3S2 3P5)
N’ = 7, 8 - N’ = 1 ® can form only one covalent bond
7 valence electrons, an atom can have maximum 1 more bond (completing the valence
orbital electron number to eight)

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 Covalent Bonding

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
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• Compound solids (about column IVA)
 Number of covalent bonds
Number of covalent bonds= 8-N’
N’= number of valence electrons

Example: Cl atom
7 valence electrons, an atom can have maximum 1 more bond (completing the valence
orbital electron number to eight)

q Covalent bonds may be extremely strong (like in diamonds) or may be

weak (like in Bismuth).Polymeric materials are covalently bonded
materials.
Electronegativity Difference Type of bond formed

0.0 to 1.4 Covalent

larger than 1.5 Ionic
%Ionic character
q Some bonds are partially ionic and partially covalent. The degree of
either bond is controlled by the electronegativities of the composing
atoms.

%ionic character = (1-e-(0.25)(X -X )2)x100 A B

(XA and XB are the electronegativities of the respective elements)

As the electronegativity difference gets higher, the bonding becomes more ionic.
 Metallic Bonding
• Valence electrons are not bound to any particular atom in the solid and they are
more or less free to move throughout the entire metal.

• Primary bond for metals and their alloys.

• The valence e- are referred as free e-.

• For metallic bonding, shared electrons are not

specific to a pair of atoms, in contrast to covalent
bonding, i.e. electrons are delocalized.

• As shared electrons are delocalized, metallic bonds are non-directional è atoms

pack closely.

• Characteristic properties of metals like high thermal and elecrical conductivities

are the result of presence of delocalized electron pool. 38
 Secondary Bonding or
Van Der Waals Bonding

• Arises from interaction between dipoles in atoms or molecules.

• Van der Waals or physical bonds, weaker in bond energy when compared with
primary bonds (0.1 eV/atom).
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 SUMMARY
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

(semiconductors, ceramics
large-Diamond
polymer chains)
small-Bismuth

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury

Secondary smallest Directional

inter-chain (polymer)
inter-molecular
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