Electronic Properties of Materials

Chapter 2
Bonding and Structure of
Molecules
1. Bond formation in s-valent dimers
2. Electronegativity scales
3. ,  and  bonds
4. Bond formation in sp-valent dimers
5. Hybrid orbitals
F2
1. Bond formation in s-valent dimers (diatomic molecules)
Let us consider two s-valent atom A and B are brought together to
form the AB diatomic molecule
Ex.: homovalent dimer H2 (with 1s valence orbitals interacting) or the
heterovalent dimer LiH (with the 2s Li valence orbital interacting with
the 1s H orbital).
A B
A near B, 2 electron
clouds of A và B
overlap
Schrödinger equation for isolated atoms A & B

2 2    
A→    A (r )  VA (r ) A (r )  E A A (r )
2m

2 2    
B→    B (r )  VB (r ) B (r )  EB B (r )
2m
Solutions for isolated atoms were solved and known.
Investigate electronic structure of molecule → wave function ,
energy E of electron
2

r12
Schrödinger equation
1
rA2 cannot be solved explicitly
rB2 → approximation method
rB1
rA1

A R B

 LCAO method: Linear Combination of Atomic Orbitals.

Wave function is linear combination of atomic wave functions:

  
 AB (r )  CA A (r )  CB B (r )
 Schrödinger equation for AB molecule:
2 2    
   AB (r )  VAB (r ) AB (r )  E AB AB (r )
2m

- When 2 atoms close together, due to interaction, the potential of

the AB diatomic molecule may be approximated by the overlapping
of the free atom A and B potentials: VAB = VA + VB.
- EA (Ex: Hydrogen 1s orbital )and EB (Ex:Lithium 2s orbital) are
energy levels of the s valence electron in atoms A and B,
respectively.
Schrödinger equation:

H  E
Solving this equation by two steps
Step 1:
- Multiply 2 sides by complex conjugation *A
- Integrate 2 sides over the space
- Transform derivative equation to algebraic equation

Step 2:
- Multiply 2 sides by complex conjugation *B
- Integrate 2 sides over the space
- Transform derivative equation to algebraic equation
Consider the AB dimer, it’s wave function ( using LCAO)
is

Where cA and cB are two constant coefficients to be determined

Schrödinger equation:

Where H is the Hamiltonian operator for the AB dimer

Multiplying by A (or B ) (* =  as  is real for s orbital) and

integrating over all space , we have secular equation:

Hamiltonian and overlap matrix elements:

 As VAB=VA + VB, the diagonal elements HAA:

The diagonal elements:

Crystal field term does not affect fundamental description of covalent bond, so:
HAA  EA
The diagonal elements HBB HBB  EB

The off-diagonal elements

or
The off-diagonal elements

where is the average value of the atomic potentials

is the average value of the energy levels

Finally, off-diagonal element is given by:

Where, h and S are the bond and overlap integrals, respectively :

The bond integral h is negative since the two positive s orbital s are
overlapping in the negative molecular potential, which represents the
covalent bond character.
The LCAO secular equation then takes the form
 is the atomic energy level mismatch which
represents the ionic bond character
where

In order to have non-trivial solution, its secular determinant must

vanish

There are 2 solutions: E

E+ : Energy level of bonding state
E- : Energy level of antibonding state

Substitute E into equation system we derive C+A, C+B, C-A, C-B; and
hence bonding wavefunction +AB, and antibonding wavefunction  -AB

Where the normalized atomic energy-level mismatch

For homonuclear diatomic molecule:

Wavefuntion of dimer AB:

The bonding and antibonding

states of a homonuclear (a) and
heteronuclear (b) diatomic
molecules are given by the
symmetric and antisymmetric
combinations of the atomic
orbitals

B3
 S-valent diatomic molecules are characterized by
bonding and antibonding states that are separated in
energy by amount wAB

For homonuclear diatomic molecules , the bonding state

has been shipted downwards by amount

The molecular eigenenergies are shifted upwards by the

amount due to overlap repulsion that reflects Pauli’s
exclusion principle
There are two key ingredients of the covalent bond:
An attractive bonding energy pulling the atoms
together
A repulsion antibonding energy keeping the atoms
apart
They are balanced at equilibrium
Case: H-H

Formation of molecular orbitals, bonding, and antibonding (ψσ and ψσ*)

when two H atoms approach each other.
The two electrons pair their spins and occupy the bonding orbital ψσ.
The PE function V in the H–H system has
positive PE contributions arising from electron–electron
repulsions and proton–proton repulsions,
negative PE contributions arising from the attractions of
the two electrons to the two protons.
- The two identical atomic wavefunctions combine in two ways to generate two
different molecular orbitals, each with a different energy.
- An atomic energy level, such as E1s , splits into two, Eσ and Eσ* .
- The splitting is due to the interaction (or overlap) between the atomic
orbitals.
- The wavefunction ψσ corresponding to the lowest electron energy is called
the bonding orbital, and ψσ* is the antibonding orbital.
+ The formation of the bond is accompanied by a redistribution of
the electronic charge
The bonding state of diatomic molecule  
AB is occupied by two
valence electrons of opposite spin.
The electronic density of the diatomic molecule will be given by
corresponding electronic charge density

The electronic density is given:

The terms i and c are the measure of the degree of ionicity

and covalency of the bond
where
and E
i 
4 h 
1/2
The terms i and c are determined by:  (E )
2 2

2
2h
c 
4 h 
1/2
 (E )
2 2

where is the normalized atomic energy-level

mismatch
-For the homonuclear diatomic molecules, the atomic energy-
level mismatch vanishes (E=0): i = 0 and c = 1
r r r r
e AB (r )  e A (r )  eB (r )  ebond (r )
The change in the electronic charge distribution on forming the
molecule is solely given by the bond charge contribution
The electronic charge has
moved from the outer region
Electronic density of the molecule into the
in a diatomic strongly attractive bond
molecule of the
same atomic type region between the atoms
This is due to the constructive
interference between the
Bond
electronic
wave function A(r) and B(r)
density that are centered on the two
atomic sited
Increased amplitude of
Electronic density wavefunction in the
of two free atoms internuclear region translates
to an enhanced probability
density (ψ2) between the
nuclei.
Hydrogen molecule
- For heteronuclear diatomic molecules:   0
r r r r r r
e AB (r )  e A (r )  ei  A (r )  eB (r )  ei B (r )  ec bond (r )
The electronic charge distribution -eAB(r) contain the ionic
contribution -eiA(r) and +eiB(r) addition to the covalent bond
charge contribution -ecbond(r)
Amplitude of the ionic charge is proportional to I
Amplitude of the covalent bond charge is proportional to c
As the energy- level mismatch (E) increases the electron spends
more time on the given A/B atom rather than being shared equally
between the two atoms in the covalent bond region.

The terms i and c are the measure of the degree of ionicity and
covalency of the bond and we have:

For the homonuclear diatomic molecules: i = 0 and c = 1

For the heteronuclear diatomic molecules, mixed covalent-ionic
character, i 0 and c 0
When E is very large, c = 0 & i = 1: pure ionic bond
2. Electronegativity
- Electronegativity, symbolized as X, is the tendency for
an atom of a given chemical element to attract shared
electron when forming a chemical bond .
Ex. Na (X =0.9)Cl (X =3.0); Ga(X =1.6)As(X =2.0);
- An atom's electronegativity is affected by both its atomic
number and the distance between valence electron and
the charged nucleus.
In an element group, electronegativity decreases as
the atomic number increases because r increases
Ex: IIA group , X(Be) = 1.5,….X(Ra) = 0.9

- The higher the associated electronegativity, the more an

atom attracts electrons. Ex. Chlorine (X=3) attaching an
e has electronic configuration like that of Ar.
 The electronegativity values for the elements.

The wider the separation (both horizontally—relative to Group

IVA—and vertically) from the lower left to the upper-right-hand
corner (i.e., the greater the difference in electronegativity), the
more ionic the bond in the diatomic molecule.
The closer the atoms are together (i.e., the smaller the difference
in electronegativity), the greater the degree of covalency.
The percentage ionic character of a bond between elements A
and B (A being the most electronegative) may be approximated
by the expression % ionic character

where XB and XA are the electronegativities for the respective

elements.
In the molecule AB: one atom can give an electron for the
other due to the difference in electronegativity.

WAB  4h 2  E 2
covalent ionic
WAB: gap between 2 bonding and antibonding levels in AB
molecule
Degree of ionicity of the s-valent bond:
Consider sp- valent octet compounds (Ex. GaAs, ZnSe),
Conduction
bands

Eg

Valence
bands
Photoemission spectroscopy (PES)
For sp- valent octet compounds, average energy gap Eg:
Eg2 = Ec2 + Ei2  Eg = (Ec2 + Ei2)1/2
Phillips - Van Vechten rule
-Average energy gap Eg or splitting between bonding and
antibonding states may be termed as the energy difference between
the centers of gravity of their valence and conduction bands
- By the above formula, Ei can be determined if Eg and Ec are known
Degree of ionicity of the bond in octet compound

Measuring Ec for elemental group IV semiconductors

and Ei for octet semiconductor compounds, i:
Ge  GaAs  ZnSe  CuBr
i = 0  0.32  0.56  0.71
Degree of ionicity increases

Cu Zn Ga Ge As Se Br

Bond in Ge purely covalent

GaAs covalent and ionic
ZnSe ionicity increases
CuBr mainly ionicity
Degree of covalence decreases, ionicity icreases
Relation between crystal structure and degree of
ionicity (Structure map Phillips - Van Vechten)
-Consider compounds with
the four-fold zinc blend or
wurtzite structure types and
the six-fold NaCl structure
type.
-The boundary is strait line
given by Ei = 1.27Ec that
corresponds to the degree of
Ei = 1.27Ec ionicity i = 0.785
-All those sp-valent octet
compounds with ionicity
larger than this critical value
are tetrahedrally coordinated.
-All those with ionicities less
than this critical value are
covalent structure types (zinc
blend or wurtzite)
-NaCl is an ionic structure
type
Wurtzite structure type Zinc-Blend structure type

AIIBVI :CdSe; CdS; ZnO AIIIBV : GaAs, GaP

Se

Wurtzite unit cell. The grey balls

represent metal atoms, and yellow
balls represent sulfur or selenium
Cd atoms.

Wurtzite unit cell

 How to determine the electronegativity?
Mulliken theory
Electronegativity of element M: XM = ½(IM + AM)
Where: I is the ionization energy, A is the electron affinity

I – energy M This can be justified as follow:

required to
dissociate an -The energy required to remove an
e- electron from neutral atom M to add into
Ionization energy (eV)
neutral atom N or vice versa: IM – AN or
N IN – AM
-Two atoms M &N would have an equal
A – energy change of atom electronegativity if IM – AN = IN – AM
when an e- is added to
then IM + AM = IN + AN
Electron affinity (eV)
From that electronegativity value is
proposed as in the above expression
 3. ,  and  bonds
- Sigma(σ) bond : This type of covalent bond is formed by the end to end
(head-on) overlap of bonding orbitals along the internuclear axis.
The electron density concentrated in region between the nuclei of the
bonding atoms:

s-s overlapping s-p overlapping

-pi(π ) bond : sideways overlap of orbitals. In the formation of π
bond, the atomic orbitals overlap in such a way that their axes remain
parallel to each other and perpendicular to the internuclear axis.
The electron density concentrated above and below the plane of the
nuclei of the bonding atoms
Sigma(σ) bond is relatively stronger π bond since the lobes point
along the molecular axis can give rise to a large overlap in the bonding
region
- Delta bonds (δ bonds) are covalent chemical bonds, where four lobes
of one involved atomic orbital overlap four lobes of the other involved
atomic orbital.
 The formation of ,  and  bonds

The z axis is horizontal for convenience in drawing bonding along

the z axis
 Molecular orbitals from d orbitals

Sigma (σ) bonding with d orbitals

Pi (π) bonding with d orbitals

Delta (δ) bonding with d orbitals

For the homonuclear diatomic molecule, a given atomic energy level
is splited into bonding and antibonding states separated by
r
h   AV B dr
h is the bond integral that couples A and B through the average
molecular potential
For a mononuclear diatomic molecule
- A and B are spherically symmetry: ss bond
- A and B are p orbitals: the three-fold degenerate free atom state
splits into the singly degenerate pp molecular state (m=0) and
doubly degenerate pp molecular states (m=1)
- A and B are d orbitals. the five-fold degenerate free atom state
splits into:
the singly degenerate dd molecular state (m=0)
two doubly degenerate dd molecular states (m=1)
two doubly degenerate dd molecular states (m=2)

For a heteronuclear diatomic molecule (TiC), the p orbitals overlap

(carbon) the d orbitals (Ti), a pd bond will be formed from the pd
(m=0) and pd (m= 1 ) states
Bonding integral

The bond integral ss , sp, pp and pp as the function
of R where 2 is the magnitude of the appropriate
valence energy level and R is internuclear separation.
- Bond integral for ss and pp are negative due to lobes of the
same sign overlapping in the negative molecular potential
- Bond integral for sp and pp are positive due to lobes of
opposite sign overlapping in the negative molecular potential
- Bond integral for pp saturates as the bond distance decreases
and changes sign at small internuclear separation because
there is more overlap between lobes of identical sign than
those of opposite sign.
- Bond integral for sp also saturates as the bond distance
decreases , since it much eventually vanish at R = 0 due to s
and p orbitals on the same site being orthogonal.
- In the vicinity of R where pp saturates:

and
4. Bond formation in sp diatomic molecules
A B

Ex.: B2, C2 N2, O2, F2

s s

 or  bonds px px
ss bond
sp bond py py
pp bond

pz pz
B4
 Schrödinger equation for electrons participating in
interactions: 
H  E
 : molecular orbital pz

Use LCAO method: linear combination of atomic orbitals

Taking z axis along the molecular axis,  wavefunction will

comprise linear combination of the As, Apz, Bs, and Bpz

  CAs As  CAp  Ap  CBs Bs  CBp  Bp

z z z z

By analogy with our previous treatment of s-valent dimer,

substituting this MO  in Schrödinger equation leads to the
LCAO secular equation
 Since the potential is unchanged with respect to inversion
about the center of the molecule:
VAB(r) = VAB(-r),
We have:
 2  2
 (r )   (r )

 
 ( r )   ( r ) Molecular wavefunction is symmetric via the
inversion about the molecular center - gerade

 
 (r )   (r ) Molecular wavefunction is antisymmetric via
the about the molecular center - ungerade

Even molecular orbital: + + s orbital

Odd molecular orbital: - + - + pz orbital

Symmetric molecular wave function:

 ( g )  CAs ( As  Bs )  CAp ( Ap  Bp )
z z z

 C As  CBs
Even g (gerade)  
C
 zAp  C Bpz

Antisymmetric molecular wave function:

 (u )  CAs ( As  Bs )  CAp ( Ap  Bp )
x z z

C As  CBs
Odd u (ungerade)  
C
 zAp  C Bpz
Secular equation for even states:
 ES  ss  E  sp   C As 
  sp   0
 EP  pp  E  C Apz 

Bond integral
Energy solutions:
1

E g  E  h  4h 2  (Esp ) 2
2

1/ 2

E p  Es
E Average value of the s and p atomic
2 energy levels

Esp is the splitting between the free atom s and p

valence energy levels
Esp = Ep- Es
 Secular equation for odd states:

 ES  ss  E sp   C As 
   0
 sp EP  pp  E  C Apz 

Energy solutions:
Eu  E  h 
1
2

4h 2  (Esp ) 2 
1/ 2

Therefore, there are 4 energy levels.

Considering two limiting cases

i. The sp splitting is large:
Thus, the free atomic s and p energy levels split
independently of each other into bonding and antibonding
states with energies and
ii. The sp spliting is small:

In case that the s and p energy levels mix together or

hybridize, we have
Bonding state:

Antibonding state:

The doubly degenerate non-bonding state:

 -For large internuclear separation R, the 
states go over to bonding and antibonding
states around the free atomic energy
up
levels Es and Ep, respectively.
-As internuclear separation R decreases,
the bond integral increases, causing
gp to decrease and s and p states to hybrid.
-As the internuclear separation decreases,
the antibonding s state and bonding p
us state tend towards the non-bonding state
-The doubly degenerate  levels, u and g
correspond to the overlap of the px and py
gs
orbitals on two atoms,
-At the large separation, they split about
the atomic p level, Ep, with a width that is
approximately half that of the  state
-The crossing of the u and upper g level
at the internuclear separation

The electronic structure of C2 has small internuclear separation

an sp-valent diatomic
F2 has large internuclear separation
molecule as function of the
internuclear separation
Arrangement of electrons in energy levels of molecules
Molecular orbital (MO) diagram for the combination of the 1s atomic orbitals
on two identical atoms (at the left) to form two MOs. One is a bonding orbital,
1s (blue), resulting from constructive interference of the 1s orbitals. The other
is an antibonding orbital, *1s (red), at higher energy resulting from
destructive interference of 1s orbitals.
In all -type MOs, the electron density is
symmetrical about an imaginary line
connecting the two nuclei.
Antibonding orbitals have nodal planes
bisecting the internuclear axis.
A node, or nodal plane, is a region in which
the probability of finding electrons is zero.
px orbitals can overlap by head-on.
This gives p and *p orbitals for the head-on overlap of
2px orbitals on the two atoms.
The side-on overlap of two corresponding 2p orbitals on two atoms
to form 2p and *2p molecular orbitals.
There is a nodal plane ( along the inter-nuclear axis for all pi
molecular orbitals.
 Formation of sp and *sp molecular orbitals in HF by overlap of
the 1s orbital of H with a 2p orbital of F.
The electronegativity difference between hydrogen ( = 2.1) and
fluorine ( =4.0) is very large (( ) = 1.9).
The bond in HF involves the 1s electron of H and an unpaired electron
from a 2p orbital of F.
The overlap of the 1s orbital of H with a 2p orbital of F to form sp and
*sp molecular orbitals.
The remaining two 2p orbitals of F have no net overlap with H orbitals.
They are called nonbonding orbitals.
Molecular orbital (MO) energy level diagram for hydrogen fluoride, HF.
E is large because the electronegativity difference is large.
H has one half-empty 1s orbital.

F has one half-empty px orbital but full py and pz orbitals. The overlap
between 1s and px produces a bonding orbital and an antibonding
orbital.
The two electrons fill the bonding orbital and thereby form a covalent
bond between H and F.
Energy level diagrams for first- and second-period homonuclear diatomic
molecules. The solid lines represent the relative energies of the indicated
atomic and molecular orbitals.
(a) The diagram for H2, He2, Li2, Be2, B2, C2,and N2 molecules.
(b) The diagram for O2, F2 and Ne2 molecules.

BOND ORDER = ½ (# of bonding electrons - # of antibonding electrons)

Bond order ?
5. Hybrid orbitals
Hybridization: The phenomenon of mixing up of atomic orbitals of
similar energies resulting in formation of equivalent number of
entirely new orbitals of identical shape and energy

The orbitals are formed by orbital hybridization is called as hybrid

orbitals.

Important points for understanding the hybridization:

(i) The number of hybrid orbitals generated is equal to the
number of pure atomic orbitals that participate in
hybridization process.
(ii) Hybridization concept is not applicable to isolated atoms. It
is used to explain the bonding scheme in a molecule.
(iii)Covalent bonds are formed by the overlap of hybrid orbitals
or of hybrid orbitals with unhybridized ones.
Consider the strongest bond g. Substitute the energy expression

into Schrodinger equation

1
Solving, we get AB:  AB  ( A   B )
2
where A, B are hybrid orbitals :

A 
1

1   sp /(1   sp )
2

1/ 2 1/ 2
 As 
1

1   sp /(1   sp )
2

1/ 2 1/ 2
 Ap x
2 2

B 
1
 
1   sp /(1  2 sp )1/ 2  Bs 
1/ 2 1
 
1   sp /(1  2 sp )1/ 2  Bp x
1/ 2

2 2
where
Wave function A has sign (+), B has sign (-) : to avoid the repulsion.

Energy of hybrid orbitals :

Energy corresponding to the hybrid wave function is smallest

Hybrid state sp : The state in which there is a combination of
different basic states s and p of electron in atom.

1
 AB  (s   pz )
2

Linear structure

Directionality
Energy corresponding to the hybrid wave function is smallest
In hybrid state → interaction between the two atoms is stronger → total
enery is reduced. In nature, most of molecules are in hybrid states.
120o

Trigonal planar
 sp3 (s+px+py+pz)

109.5 o

Tetrahedral structure

(a) Si is in Group IV in the Periodic Table. An isolated Si atom has two electrons
in the 3s and two electrons in the 3p orbitals.
(b) When Si is about to bond, the one 3s orbital and the three 3p orbitals become
perturbed and mixed to form four hybridized orbitals, hyb, called sp3
orbitals, which are directed toward the corners of a tetrahedron.
-The sp3 orbital has a large major lobe and a small back lobe.
-Each sp3 orbital takes one of the four valence electrons.
sp3 hybridization

The 3s and 3p energy levels are quite close, and when five
Si atoms approach each other, the interaction results in the
four orbitals  (3s),  (3px),  (3py) and  (3pz) mixing
together to form four new hybrid orbitals, which are
directed in tetrahedral directions; that is, each one is
aimed as far away from the others as possible.
The energy of the hybrid orbital is the linear average of the
starting orbitals: