Chemical Bonding

Introduction
¾ Atoms are able to combine to form aggregates
¾ Bond formation involves liberation of energy
¾ Bonding forces are essentially electrostatic (Coulombic)
¾ Chemical bonding is an indispensable concept for explaining the cohesion of
materials and it has a fundamental influence on materials properties
e.g.: diamond is hard but graphite is soft
Bonding forces and energies
¾ The repulsion between atoms, when they are brought close to each other, is
related to the Pauli principle: when the electronic clouds surrounding the atoms
start to overlap, the energy of the system increases abruptly
ƒ Repulsive force shoot-up as interatomic distance tends to zero
ƒ At larger Interatomic distance repulsive force is negligible i.e. they are short-
range
¾ The origin of the attractive part, dominating at large distances, depends on the
particular type of bonding

¾ Net force, FN = FA + FR
¾ Net energy, EN = EA + ER
 +
Attractive force FA

Attraction
Force F

0
Interatomic separation r
Repulsive force FR
Repulsion

(a)
r0

Net force FN (a) T he dependence of repulsive,

attractive, and net forces on
interatomic separation for
two isolated atoms. (b) The
equilibrium dependence of repulsive,
attractive, and net potential
+ energies on interatomic
separation for two isolated
Repulsion

Repulsive energy ER atoms.

Potential energy E

Interatomic separation r
0
(b) Net energy EN
Attraction

E0

Attractive energy EA

¾ This is typical potential well for two interacting atoms

 r
E N = ∫ FN dr
∞

A B
=− +
rm rn

Bond Length and Bond Energy

¾ Bond length is given by the equilibrium
∂E N
= 0 , at which FA = −FR, so that FN = 0
∂r 1/( m − n )
⎡ mA ⎤
and r0 = ⎢
⎣ nB ⎥⎦
which is the centre-to-centre distance of the bonding pair of atoms

¾ Bond energy (E0) is the potential energy at r0, that corresponds to the minimum
¾ For EN to show a minimum, n > m
¾ E0 is always −ive

¾ Stronger bonds have smaller bond lengths (1—2 Å)

¾ Weaker bonds have larger bond lengths (2—5 Å)
¾ Diatomic chlorine: bond length is 1.98 Å
Bonding Types
¾ Primary bonding and Secondary bonding
¾ Three types of primary bonding: Covalent, Metallic, and Ionic
ƒ Electrons are transferred or shared
ƒ Primary bonding is bonding between atoms and ions
Stronger (100—1000 kJ/mol or 1—10 eV)
ƒ Covalent: electrons are shared between the molecules, to saturate the valency
Example - H2
ƒ Ionic: Strong Coulomb interaction among negative atoms (have an extra electron
each) and positive atoms (lost an electron). Example - Na+Cl-
ƒ Metallic: the atoms are ionized, loosing some electrons from the valence band.
Those electrons form a electron sea, which binds the charged nuclei in place

covalent

Semiconductors

Polymers

metallic secondary

Metals
ionic Ceramics and glass
¾ Secondary Bonding
ƒ No electrons are transferred or shared
ƒ Bonding between molecules
Weaker (< 100 kJ/mol or < 1 eV)
ƒ Due to interaction of atomic/molecular dipoles
ƒ Fluctuating induced dipole in molecular crystals (inert gases, H 2, Cl 2…)
ƒ Permanent dipole bonds (polar molecules - H2O, HCl...)
ƒ Polar molecule-induced dipole bonds (a polar molecule induces a dipole in a
nearby nonpolar atom/molecule)

B onding E nergies and M elting Temperatures for V arious S ubstances

Bonding Energy Melting
kJ/mol eV/Atom, T emperature
Bonding Type Substance (kcal/mol) Ion, Molecule (ⴗC )
NaCl 640 (153) 3.3 801
Ionic
MgO 1000 (239) 5.2 2800
Si 450 (108) 4.7 1410
Covalent
C (diamond) 713 (170) 7.4 ⬎3550
Hg 68 (16) 0.7 ⫺39
Al 324 (77) 3.4 660
Metallic
Fe 406 (97) 4.2 1538
W 849 (203) 8.8 3410
Ar 7.7 (1.8) 0.08 ⫺189
van der Waals
Cl2 31 (7.4) 0.32 ⫺101
NH3 35 (8.4) 0.36 ⫺78
Hydrogen
H 2O 51 (12.2) 0.52 0
Covalent bonds
¾ Sharing of a pair of electrons between two atoms so that the inert gas type ns2np6
outer electron configuration is achieved
¾ The electrons spend more time in between the nuclei than outside, thus producing
bonding
¾ By doing so energy is lowered
¾ Atoms must have at least one half-filled orbital
¾ Electron may get promoted to higher levels by hybridization—leaving many outer
orbital unpaired
¾ Can be described by orbital overlap
¾ Directional: direction of the bond is in the direction of greatest orbital overlap
¾ Examples:
ƒ Many nonmetallic elemental gas molecules: H2, N2, O2, Cl2
ƒ Molecules containing dissimilar atoms: CH4, H2O, HNO3
ƒ Solids like diamond, graphite, germanium, silicon, SiC, GaAs, etc.
In these solids atoms are arranged in a non-close-packed manner

¾ Covalent bond model: an atom can covalently bond with at most 8-N, N = number
of valence electrons
¾ Example: formation of Cl2
2 5
ƒ Cl: [Ne] 3s 3p , we have N=7, so that only 1 covalent bond
¾ Example: formation of C compounds
2 2
ƒ C: [He] 2s 2p , we have N=4, so that there ar 4 covalent bonds possible
 Cl Cl Cl Cl

(a) (b) (c) (d)

The covalent bond in a molecule of chlorine gas, C l2 , is illustrated with (a) a plane tary
model compared with (b) the actual electron density and (c) an “electron-dot” schematic
and (d) a “bond-line” schematic.

H Schematic representation of covalent

bonding in a molecule of methane (C H 4 ).
S hared electron
S hared electron from carbon
from hydrogen

H C H

H
 H H

C C

H H C
Ethylene C
molecule C C
C
(a)
C

C C
H H H H H H H H C
.... .... C
C C C C C C C C C
C
H H H H H H H H C
C C

Ethylene
Three-dimensional structure of bond-
mer ing in the covalentsolid, carbon (diamond).
E ach carbon atom (C ) has four covalentbonds
.... Polyethylene .... to four other carbon atoms.
molecule I n this illustration, the “bond-line”
(b) schematic of covalentbonding is given
a perspective view to emphasize the spatial ar-
(a) An ethylene molecule (C 2 H 4 ) is compared rangementof bonded carbon atoms.
with (b) a polyethylene molecule ( C 2 H 4 ) n thatre-
sults from the conversion of the C = C double bond into
two C — C single bonds.
 H ....
H C
H C H

.
H H

...
C H H
. H H H H H
... H H
C
C C H C
C C C C H H
H C H H C H
C H H H C H
H H H H C H
H C
H C HH H H C ....
C H
H H
C H H H H H
H HH C H
C H H
C C C C
C C
H H H H H H C H
H H
H C H H C H H .
H ...
H H H H C H C H H C
H H H
H H C C
.... C C C H C H H
C C H
C C H C H
H H H H
H H H H C H H
H
C H
H C H H
H H C
H H H H H
H C H
H
C C
C C H H H H C H
C C C
.... C H H C C H C H
H H H H
H H
H H

....
Two-dimensional schematic representation of the “spaghettilike” structure of solid polyethylene.
 ¾ Bonds may be single, double, triple, etc.
¾ Bond length decreases as the multiplicity of bonds (bond order) increases, i.e a
double bond is shorter than a single bond between same pair of atoms.
C—C = 1.54 Å, C═C = 1.34 Å
¾ Bond strength also increases as the bond order increases
C—C = 346 kJ/mol, C═C = 602 kJ/mol
¾ The potential energy of a system of covalently interacting atoms depends not only
on the distances between atoms, but also on angles between bonds
Metallic bonds
¾ Metals are good conductors of heat and electricity, opaque, lustrous, and malleable
¾ In metals, the atoms are ionized, loosing some electrons from the outer shell
¾ Those electrons form an electron sea or gas, which binds the aggregate of charged
nuclei
¾ Electron gas holds the positive ion core together
¾ Bonding electrons are not localized anymore
¾ Electrons are free to move through the solid (free electrons, thus good electrical
and thermal conductivity)
¾ Free electrons absorb energy (thus metals are opaque)
¾ Electrons remit the energy (metals are lustrous)
¾ Metallic bonds are non-directional (explains why metals are malleable)
¾ Non-directional bonds also make each metal atom tends to be surrounded by as
many atoms as possible (close packing)
 Electron cloud from valence electrons

Cu 2+ ion core
(cutaway view)

Metallic bond consisting of an electron cloud,or gas. An imaginary

slice is shown through the front face of the crystal structure of copper, reveal-
ing Cu 2+ ion cores bonded by the delocalized valence electrons
.
 ¾ Elements like Na, K, Cu, Ag, Au are very metallic
¾ Elements like Nb, W, V, Ti are more metallic + some covalent nature (so they have
high melting point)
¾ As, Se, etc: More covalent + partly metallic

¾ Elements of the IVA group of the periodic table

ƒ C in diamond form highly covalent bonds
ƒ Si, Ge are partly metallic + partly covalent
ƒ Sn: two forms one form of Sn (α) is mostly covalent and other (β) is mostly
metallic
ƒ Pb is metallic

Ionic bonds
¾ Mutual ionization of atoms that differ vastly in their electronegativity occurs by
electron transfer
ƒ Electron transfer reduces the energy of the system of atoms, that is, electron
transfer is energetically favourable
ƒ Less electronegative atom donates electrons becoming a cation
ƒ More electronegative atom accepts electrons becoming an anion
ƒ Ionic substances are electrically neutral
ƒ Ions are attracted by strong coulombic interaction
ƒ Note relative sizes of cation and anion
 Na
Coulombic bonding force
Cl

Na + Cl⫺ Na + Cl⫺ Na +

Cl⫺ Na + Cl⫺ Na + Cl⫺

Na + Cl⫺ Na + Cl⫺ Na +

Cl⫺ Na + Cl⫺ Na + Cl⫺

Na +
Na + Cl –
Cl –
Formation of an ionic bond between sodium and chlorine in
which the effectof ionization on atomic radius is illustrated. The cation
(N a+ ) becomes smaller than the neutral atom (N a), while the anion rNa + rCl –
(C l− ) becomes larger than the neutral atom (C l).
a0
¾ An ionic bond is non-directional because field of attraction between ions has a
spherical symmetry
¾ As a result smaller cations tend to be surrounded by as many anions as possible
(close packing)
¾ Coordination number (CN) is of a cation is determined by radius ratio rc/ra

¾ For ionic bonds (existing in isolated molecules): EN = − A

r
+ Bn + ∆E
r
A = 1 Z1Z2e2
4πε 0
ε 0 is permittivity of vacuum, 8.85x10−12 F/m
Zi is the valence
e is the electronic charge
∆E =[IEcation+ EAanion]/mol of bond
n = is a constant, whose value is approximately 8
B = is a constant, whose value depends on the material

¾ An ion in a crystal interacts with all other ions in the neighbourhood

¾ Coulomb term must be multiplied by a geometric constant (known as Madelung
constant) in order to get the right energy term in crystal
ƒ For NaCl crystal: 1.748
ƒ For CsCl crystal: 1.763

learn more about Madelung constatnts @ https://tinyurl.com/yykm765j

 Coordination Numbers and
Geometries for Various Cation –Anion
Radius Ratios (rC /rA )
Coordination Cation– Anion Coordination
Number R adius R atio Geometry

2 ⬍0.155
Ionic Radii for Several Cations and Anions
(for a Coordination Number of 6)
Ionic Radius Ionic Radius
Cation (nm) Anion (nm)
3 0.155– 0.225 Al 3⫹ 0.053 Br ⫺ 0.196
Ba 2⫹ 0.136 Cl ⫺ 0.181
Ca 2⫹ 0.100 F⫺ 0.133
Cs ⫹ 0.170 I⫺ 0.220
4 0.225– 0.414
Fe 2⫹ 0.077 O 2⫺ 0.140
Fe 3⫹ 0.069 S 2⫺ 0.184
K⫹ 0.138
Mg 2⫹ 0.072
Mn 2⫹ 0.067
Na ⫹ 0.102
6 0.414– 0.732
Ni 2⫹ 0.069
Si 4⫹ 0.040
Ti 4⫹ 0.061

8 0.732– 1.0
https://www.tulane.edu/~sanelson/eens211/paulingsrules.htm
 R = 1.0
r = 0.2

CN = 1 possible CN = 2 possible CN = 3 maximum CN = 4 unstable

The largestnumber of ions of radius R thatcan coordinate an atom of radius r is 3 when the ra-
dius ratio, r/R=0.2 . (N ote: The instability for C N = 4 can be reduced butnot eliminated by allowing a
three-dimensional, rather than a coplanar, stacking of the larger ions.)
R r
cos 30° = 0.866 = → = 0.155
r+R R

30°

The minimum radius ratio, r/R ,

thatcan produce threefold coordination
is 0.155.
 ¾ Ionic materials have relatively high bond energy ; vary from 600—1500 kJ/mol
ƒ For NaCl: ∆E = 496−343 = 153 kJ/mol of bond
ƒ Bond energy Er is −640 kJ/mol of NaCl
0

¾ In ceramics major bonding is ionic

Ionic character of a covalent bond

¾ Chemical bonds are often mixed type

¾ For a covalent bond the fractional ionic character is given by

⎛ ⎞
fi = 1− exp ⎜⎜ −0.25(∆EN)2 ⎟⎟
⎝ ⎠

¾ For crystals of the type ANB8-N,

⎛ N ⎞ ⎛ Nf ⎞
fic = 1− ⎜ ⎟ + ⎜⎜ i ⎟
⎟
⎜ M⎟ ⎜ M ⎟
⎝ ⎠ ⎝ ⎠

N is number of valence electrons of B

M is the coordination number
Ionic, Covalent, and Metallic radii
¾ Ionic radius (Goldschmidt radius) of anion (ra) + Ionic radius of cation (rc) = ionic
bond length
¾ Covalent radii: One half of the covalent bond length (single bond is assumed)
ƒ Covalent radii is additive, provided a single electron pair is shared
ƒ i.e. 0.5(C—C) in diamond +0.5( Si—Si) in Silicon crystal = Si—C
¾ Metallic (atomic) radius = 0.5*(nearest neighbour distance in crystals)
Radii of selected elements (in Å)
Element Atomic Covalent Ionic radius
radius radius
Fe 1.241 1.16 0.69 (Fe3+, CN6)
(bcc) 0.77 (Fe2+, CN6)
Al 1.432 1.25 0.39 (Al3+, CN4)
0.53 (Al3+, CN6)
Zn 1.335 1.25 0.60 (Zn2+ , CN4)
0.70 (Zn2+, CN6)
Na 1.858 1.57 0.99 (Na+, CN4)
1.02 (Na+, CN6)
C 0.772 0.77 0.15 (C4+, CN4)
(dia)
Si 1.176 1.17 0.26 (Si4+, CN4)
0.40 (Si4+, CN6)
Cl 0.994 0.99 1.81 (Cl−, CN6)
¾ Ferric ion is smaller than Ferrous ion
¾ For Si and C covalent radii is same as atomic radii
¾ For metals covalent and atomic radii are different
Secondary Bonds: Permanent dipole bonds
O

H H

+ +

Dipole

Hydrogen Bonding in Water

¾ Dipole exists in polar molecules due to EN difference in covalently bonded atoms
(H2O, NH3, HCl, etc.)
¾ Weaker bonding between molecules due to attraction between permanent dipoles
¾ Bond energy is 51 kJ/mol for “hydrogen bonds” in H2O
¾ Dipole moment, D=1.85 Debye for H2O
¾ These bonds are directional

Crystal structure of Ice

 Snow Flakes (note the hexagonal symmetry)

Polymer chains held together by hydrogen bonds

 ¾ Polymers/Plastics: strong covalent bonding within the molecules, weak secondary
bonding between the polymeric molecules
¾ Important factor in determining the structure and properties of many organic
materials, including DNA.

Secondary Bonds: Induced dipole bonds

¾ A weak type of attraction exists between all atoms and molecules
¾ Its is due to momentary fluctuation of electron density around an atom, inducing
transient dipoles
¾ These attractive forces are important in those solids were other type of bonding is
impossible
Example: inert gas crystals, molecular crystals of diatomic gases (when motifs are
held together by weak induced dipole bonds, we call the solid molecular crystals)
¾ Bonding is not directional
¾ Weaker than permanent dipole bonds
Variation in Bonding Character and Properties
¾ Melting and boiling involves rupturing of bonds
¾ As bond strength increases melting point and boiling point also increases
¾ When a solid consist of molecules held together by secondary bonds, their melting
and boiling involves breaking of weaker secondary bonds.
¾ For example, melting point of polymers are quite low compared to metals

¾ Thermal and electrical conductivities dependent on number of free electrons

¾ Thermal expansion of strongly bonded materials are less

¾ Mechanical properties also depend on strength of bonds, as well as directional

nature of bonding
¾ Covalently bonded diamond is hard and brittle, metals are soft, ductile and
malleable, ionic compounds are in between
Band Structure Model of Solids
¾ Electrical conductivity of materials is due to:
ƒ mobility of electrons Ö electronic conduction, e.g. metals
ƒ mobility of ions Ö ionic conduction, e.g. molten salts

Electrical conductivity (Siemens/m) varies between different materials by over 27 orders

of magnitude, the greatest variation of any physical property

How are the energy levels or bands created in solids?

¾ In isolated atoms electrons occupy well defined orbitals (energy states)
¾ As large number of atoms (about N=6×10+28/m3) are brought closer to form a solid,
Coulomb forces cause their orbitals to interact producing energy states that differ
from those in the isolated atoms
¾ A collection of such closely spaced discrete energy level resulting from interaction
between orbitals of a particular energy is known as a band
 S chematic plot of
electron energy versus 2 s Electron
energy band
2 s Electron state
interatomic separation (12 states)

for an aggregate of 12
Individual allowed energy states

Energy
atoms (N ⫽ 12). Upon
close approach, each of
1 s Electron state
the 1s and 2s atomic 1 s Electron
energy band
states splits to form an (12 states)

electron energy band

consisting of 12 states.
Interatomic separation

ƒ 2s electron states give rise to N discrete energy states forming 2s band

ƒ Similarly, 2p orbitals give rise to 3N discrete energy states in the corresponding
band

¾ Number of discrete energy levels within a band increases as the number of atoms
increases—band becomes nearly continuous
¾ But width of the band at a given interatomic distance is unaffected by the number
of atoms involved
¾ Like in orbitals, each of the individual states in a band can have a maximum of two
electrons, but with opposing spins (Pauli exclusion principle)
 3s
3s
2p
2p
2s
2s
1s
1s

Isolated Na atom
Hypothetical Na4 molecule
Energy-
level diagram for Energy-level diagram for a hypotheti-
an isolated sodium cal N a4 molecule. The four shared, outer orbital
atom. electrons are “split” into four slightly different
energy levels, as predicted by the Pauli exclusion
principle.
 3s valence band
(half-filled)
2p
2s
1s

.... ....

....

....
Na solid
Energy-level diagram for solid sodium. The discrete 3s energy level
of previous figure has given way to a pseudocontinuous energy band (half-filled).
Again,the splitting of the 3s energy level is predicted by the Pauli exclusion principle.
¾ Distribution of electrons in the bands determines the electrical properties of solids
¾ For inner electron states, band formation may not take place at equilibrium inter
atomic separation
(a) (b)

Energy band
Energy

Energy band gap

Energy band

Energy
Interatomic
separation
Equilibrium
interatomic
spacing

(a) The conventional representation of the electron energy band

structure for a solid material at the equilibrium interatomic separation.
(b) Electron energy versus interatomic separation for an aggregate of atoms,
illustrating how the energy band structure at the equilibrium separation in (a) is
generated.
¾ Energy bands of adjacent states may overlap
 ¾ Band gap is created when energy states of adjacent bands do not overlap at
equilibrium interatomic distance
ƒ Electrons are not allowed to have an energy state in the band gap regime
(forbidden band)

¾ As T→0 K
ƒ All electrons from a specific orbital is accommodated within the energy states of
the corresponding band
ƒ The highest energy band that is full or partially filled is called the valence band
ƒ Fermi Energy (Ef) – energy of highest filled state
ƒ The energy bands below valence band are completely filled and those above are
empty

Metals, Semiconductors, and Insulators

¾ Electrical conduction requires that electrons be able to gain energy in an electric
field
¾ Metals have either empty states in the valence band (Cu, Ag, Au, Al, etc.) or have
overlapping valence band and conduction band (Mg, Be, Bi, Sb, As, Cgraphite…) at 0 K
¾ Under an applied electric field, valence electrons in metals are promoted into
conduction band, that starts infinitesimal above the Fermi level, resulting in
conductivity
¾ Metals can conduct electricity even at 0 K
¾ Conductivity of metals decreases as T ↑
 Empty
Empty conduction Empty
band Empty band conduction
band band

Ef B and gap
B and gap B and gap

Empty states Filled Filled Filled

Ef band valence
valence
band band
Filled states

(a) (b) (c) (d)

The various possible electron band structures in solids at 0 K . (a)

The electron band structure found in metals such as copper, in which there are
available electron states above and adjacent to filled states, in the same band.
(b) The electron band structure of metals such as magnesium, wherein there is
an overlap of filled and empty outer bands. (c) The electron band structure
characteristic of insulators; the filled valence band is separated from the empty
conduction band by a relatively large band gap (⬎2 eV ). (d) The electron band
structure found in the semiconductors, which is the same as for insulators except
that the band gap is relatively narrow (⬍2 eV ).

¾ In semiconductors and insulators, the valence band is fully filled, and no more
electrons can be added
¾ The allowed band that is just above the valence band is known as the conduction
band
¾ Energy difference between the valence band and the conduction band is known as
the band gap energy (Eg)
¾ In semiconductors and insulators, electrons have to jump across the band gap into
conduction band to find conducting states above Eg
¾ The energy needed for the jump may come from thermal or electromagnetic
sources
¾ A working definition for the difference between semiconductors and insulators is
that in semiconductors, electrons can reach the conduction band at ordinary
temperatures, where in insulators they cannot
ƒ The probability that an electron reaches the conduction band is about
exp(-Eg/2kT)
ƒ If this probability is, say, < 10−24 one would not find a single electron in the
conduction band in a solid of 1 cm3
ƒ This requires Eg/2kT > 55
ƒ At room temperature, 2kT ≅ 0.052 eV; thus Eg > 2.8 eV can be used as the
condition for an insulator
ƒ Band gap in Cdiamond is 5.4 eV, Si 0.7 eV, Ge 1.1 eV
¾ Conductivity of a semiconductor increases as T ↑
¾ An electron promoted into the conduction band leaves a hole (positive charge) in
the valence band, that can also participate in conduction
¾ Holes exist in metals as well, but are more important in semiconductors and
insulators
¾ Conductivity of pure Si (group IVA) is quite low at ambient temperatures (<5×10−4)
¾ Can be increased by doping
¾ Doping increases carrier concentration
ƒ n-type: Si doped with P (group VA)
ƒ p-type: Si doped with Al (group IIIA)
ƒ Many compounds of IIIA-VA are also semiconducting: GaAs, InP, etc.

¾ A simple change in crystal structure can sometime change the electrical nature.
Gray tin (stable form below 13.2°C) is semiconducting (Eg is 0.08 eV), whereas
white tin (stable form above 13.2°C) is metallic
¾ VO2 is a conductor above 66°C, whereas it is an insulator below this temperature
ƒ Can be attributed to crystal structure changes

¾ One may make an insulator conducting by applying high pressure