ELECTRONS, BONDING,

PROPERTIES

Electron in atoms, electronic states&configurations

What promotes bonding?

Types of bonds

What properties can be deduced from bonding?

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Physical Mechanical Electrical Optical Thermodynamic
 What is the origin of materials properties?

Physical Mechanical Electrical Optical Thermodynamic

 Quantum mechanics

Electronic configuration
QM
Valence electrons
Electro negativity
Bonding characteristics
(metallic, covalent, ionic (primary) Van der Waals (secondary)

Structure

Physical Mechanical Electrical Optical Thermodynamic

density strength resistivity Characteristic Melting
Spectrum temperature
reflectivity
Limits of classical physics
=> quantum mechanics
 Electrons in Atoms
Early 20th century some phenomena could not be explained by
classical mechanics:

-why are atoms empty

hv>EI
-photo electric effect
 Photo Electric Effect
Interaction between photons and electrons (in condensed matter)
Discovered by Heinrich Hertz
Explained by Albert Einstein, noble price in physics 1921
photons, light of discrete energy quantities, E=hv \
=> electrons on discrete energy levels

IZ

e- emission

hv>EI
e- emission

IZ

IZ
Intensity
 Electrons in Atoms
Early 20th century many phenomena could not be explained by
classical mechanics:

-photo electric effect

hv>EI
-why are atoms empty

Bohrs model: quantization of energy

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 Electrons in Atoms- Bohrs Model
Bohrs model: involves only some aspects of QM like quantization of energy, very simple, mainly
used for hydrogen

Can explain:
Photo electric effect
discrete absorption spectrum
of atoms E=hv

Can not explain:

-emptyness,
-stability of atoms
(radiation losses, accelerated charge
hv> W
emits electromagnetic radiation,
P=2/3 q2/c3 a2, Lamors equation)

Quantum mechanics (wave mechanical model)

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 Wave Mechanical Model
Electrons have wavelike and particulate properties.
This means that electrons are in orbitals defined by a probability

Bohr vs. Wave Mechanical Model

-no more emptiness

-no radiation losses which would cause instability Meng286
 Quantum Numbers-Electronic Structure
Each orbital at discrete energy level determined by four quantum numbers
n = principal, describes size of atom, energy of an orbital, K, L, M, N, O (1, 2,
3, ...)

l = angular, shape of orbitals, s, p, d, f (0, 1, 2, 3,, n -1)

spherical polar cloverleaf

ml = magnetic, orientation in space, 1, 3, 5, 7 (-l to +l)

ms = spin, , -
Quantum Numbers

n: K, L, M, N, O (1, 2, 3, etc.)
l: s,p, d, f (0, 1, 2, 3,, n -1)
m:1, 3, 5, 7 (-l to +l)
, -

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 Single electron orbitals
Orientation in space
m

l
 Electron Energy States: How do
electrons occupy orbits
Electrons...
Tend to occupy lowest available energy state
Two electrons can not have same quantum numbers
(Pauli exclusion principle) K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n -1)
1, 3, 5, 7 (-l to +l
4d , -
4p N-shell n = 4
~Size and
symmetry 3d
Energy

4s

3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d 5s
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Electron configuration stability

N
O

Be C

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 SURVEY OF ELEMENTS
Most elements: Electron configuration not stable (benefit from a reaction).

Element Atomic # Electron configuration

Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

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Electron configuration => Periodic table

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 SURVEY OF ELEMENTS
Most elements: Electron configuration not stable (benefit from a reaction).

Element Atomic # Electron configuration

Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

Why? Valence (outer) shell usually not filled completely

If outer shell not filled completely valence electrons at a higher
energetic level Meng286
Electron configuration => Periodic table

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 Electron Configurations
Valence electrons those in unfilled shells
Filled shells more stable
Valence electrons are most available for
bonding and tend to control the chemical
properties

example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons
Filled k-shell
with 2 electrons Unfilled l-shell
With 4 electrons
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 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

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 Electronegativity
tendency to attract electrons
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd
edition. Copyright 1960 by Cornell University.
Electron configuration stability
aquire electrons to become more stable
(reduce potential energy)

Give electrons to become more stable

F
(reduce potential energy)
N
O Cl

Be C

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The Periodic Table: Aspects for Bonding
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.
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From electron configurations to bonds

Valence electron configuration defines bonds

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 Ionic Bonding
Large difference in electronegativity required.
metal donates electrons, non-metal accept electrons
Requires electron transfer.
Occurs between + and - ions.
q1q2
Bonding strength is of electrostatic nature, F = k
r2
Example: NaCl

Na (metal) unstable
1s22s22p63s1 Cl (nonmetal) unstable
1s22s22p63s23p5
Ne stable electron

Na (cation) stable + -
Cl (anion) stable
Like neon 1s22s22p6 Like argon 1s22s22p63s23p6
qq Coulombic
Fc = k1 2 Attraction
c 2
r
 IONIC BONDING
Energy minimum energy most stable
Energy balance of attractive (between ions) and
repulsive (orbit overlap) terms A B
EN = EA + ER =
r rn
Repulsive energy ER

r0 (T) stable interatomic spacing

Interatomic separation r

Net energy EN

E0 : bond energy
Attractive energy EA
 Examples: Ionic Bonding
Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd
edition. Copyright 1960 by Cornell University.
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 Covalent Bonding
similar electronegativity, share electrons
bonds determined by valence s & p orbitals dominate bonding
Example: CH4 (methane) also diamond

shared electrons
H
C: has 4 valence e-, from carbon atom
CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

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 Bond Hybrization
Carbon can form sp3 hybrid
orbitals

Fig. 2.13, Callister & Rethwisch 9e. 32

 Covalent Bonding: Carbon sp3
Example: CH4

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 Covalent Bonding
Electrons are strictly localized in covalently bonded matter
Typically covalent bonding is directional (due to shape of
orbitals)

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 MIXED NATURE: IONIC-COVALENT
Continuous spectrum from ionic to covalent (conquer to sharing)

Ionic-Covalent Mixed Bonding

% ionic character I= C
C&I
where XA & XB are Pauling electronegativities (X A X B )2

4
x (100 %)
1 e

Ex: MgO XMg = 1.3
XO = 3.5
(3.5 1.3 )2

% ionic character = 1 e 4 x (100%) = 70.2% ionic


 Metallic Bonding
Between atoms with a small number of electrons in their valence shells
If those atoms come together electrons share orbitals (many as oppose to covalent bonding)
=> Electrons stray easy throughout the lattice (become delocalized) as oppose to ionic or
covalent bonds

Metallic bond is electrostatic attraction between delocalized

electrons and metallic ions Meng286
 Primary Bonding
Metallic Bond: delocalized as electron cloud
Ionic bond: electrostatic attraction between charged ions
Covalent bonds: localized shearing of electrons
Continuous spectrum from ionic to covalent (conquer to sharing)
Strong!

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 SECONDARY BONDING
Arises from interaction between dipoles

Permanent and fluctuating dipoles

Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

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SECONDARY BONDING- DIPOLE DIPOLE
INTERACTION

Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

secon
-ex: polymer dar y
bo n d secondary bonding
in g

Secondary bonding is weakest bond

Secondary bonding between fluctuating dipoles is smaller than
between permanent dipole-molecules
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 Summary: Bonding
Type Bond Energy Comments
Ionic Large! (ceramics)

Covalent Variable Directional

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

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
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 PROPERTIES FROM BONDING
Energy

ro
r
Eo =
bond energy
E0 T (vibrational energy overcomes a lower E
m 0 easier)
E0 (bonds have to be broken)
E0 1/ (potentialdEbecomes more symmetric)
E0 E (slope E, dr E and E)
0

Also: metallic (free electrons) vs. ionic/covalent (localized)

-metallic high

electrical conductivity (free electrons)
high
-metallic conductivity (free electrons transport heat) (diamond exception)
thermal
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 Examples, Tm
Ceramics:
Diamond (covalent): Tm = 3550 C
Al2O3 (ionic) : Tm = 2050 C

Metals (metallic):
W: 3410 C
Hg: -40 C

Polymers (Van der Waals):

PVC: ~200 C

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 Meng286
M.F. Ashby, Transactions of the Royal Society a-, 2006. 364(1838): p. 15-30.
 Properties From Bonding: Tm
Bond length, r Melting Temperature, Tm
Energy
r

Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo= Tm is larger if Eo is larger.
bond energy

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 Properties From Bonding:
Coefficient of thermal expansion,
length, Lo coeff. thermal expansion
unheated, T1
L L
= ( T2 - T1)
heated, T2 Lo

~ symmetric at ro
Energy
unstretched length
ro
r is larger if Eo is smaller.

Eo
larger

Eo smaller
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 Summary:
Electronic configuration -> valence electrons -> binding -> properties

Ceramics Large bond energy

(Ionic & covalent bonding): large Tm
large E
small

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
secon
d ar y b
o n d in small E
g
large