Topic 1: Chemical bonding

OUR FOCUS

Penetration and
shielding - effective
nuclear charge

Atomic parameters - atomic and ionic radii

- ionisation energy
- electron affinity
- electronegativity
- polarisability
 Penetration and shielding effect
Write the electronic configuration for Li.

1s2 2s1 or 1s2 2p1 Why?

• Shielded - 2s & 2p orbitals Radial probability

are larger than 1s orbital,
therefore an electron in either
orbital is “shielded” from 1s
attractive force of nucleus by
the 1s electron.

• Penetrated – electron from 2p 2s

2s orbital can go inside of 1s
orbital. How?

Distance from nucleus

 Effective Nuclear Charge

Effective nuclear charge (Zeff) is the “positive charge” felt by

an electron.

Zeff = Z -  0 <  < Z ( = shielding constant)

(Z = atomic number)

Slater's rule is used to determine the value of 

 Calculating Zeff
• Formula Zeff = Z-
(Z = atomic no.) and ( = shielding constant)

• Arrange sets according the quantum number, n

[1s] [2s,2p] [3s,3p] [3d] [4s,4p] [4d] [4f]

• Slater’s Rules
Electrons in the same group as the electron of interest shield to
an extent of 0.35 nuclear charge units.

If the electron of interest is an s or p electron: All electrons with

one less value of the principal quantum number shield to an
extent of 0.85 units of nuclear charge. All electrons with two less
values of the principal quantum number shield to an extent of
1.00 units.
 Calculating Zeff

If the electron of interest is an d or f electron: All electrons to

the left shield to an extent of 1.00 units of nuclear charge.

Bear in mind that according to Slater’s rule, only one electron

is been shielded!

Now let’s apply these rule shall we?

• Calculate Zeff for a valence electron in F

Z = 9, so (1s2)(2s2, 2p5),
Thus: Zeff = 9 - [(0.85 x 2)+(0.35 x 6)]
= 9 - 3.8
= 5.2
Meaning: The last electron is held ~ 58% of the force
expected for a +9 nucleus and a -1 electron.
• Calculate Zeff for a 4s and a 3d in Zn:

Electronic configuration for Zn:

(1s2) (2s2, 2p6) (3s2, 3p6) (3d10) (4s2)

For a 4s electron:
Establish the shielding constant for the 4s electron
S = (10 x 1.00) + (18 x 0.85) + (1 x 0.35) = 25.65

Calculate the effective nuclear charge

Zeff= Z- = 30 - 25.65 = 4.35

For a 3d electron:
S = (18 x 1.00) + (9 x 0.35) = 21.15
Thus the Zeff for 3d is:
Zeff= Z-s = 30-21.15 = 8.85

So what is the conclusion we can make from these values

between 4s and 3d ???

Zeff for 4s electron = 4.35 < Zeff for 3d electron = 8.85

Meaning: 3d electrons experience a much greater positive

charge than the 4s electron and would be held more tightly.
Thus, the 4s electrons will be the first removed when Zn is
ionised.
 Effective Nuclear Charge (Zeff)

increasing Zeff
increasing Zeff
 ATOMIC AND IONIC RADII

• The sizes of atoms & ions are also related to the

ionisation energies and electron affinities.
• As the nuclear charge increases, the electrons are
pulled in towards the centre of the atom , and the size
of any particular orbital decreases
• Increasing number of electron will keep the outer
orbital large.
• The interaction of this two effects (increasing nuclear
charge and increasing number of electrons) results in
a gradual decrease in atomic size across each
periods.
 Atomic Radii

covalent radius

One-half the distance

metallic radius between the centres of
atoms in the molecule
One-half the distance
between centres of two
adjacent atoms in metals.
 Ionic radius

Cl
Na+ Cl-
Na

Cation is always smaller than atom from which it

is formed.

Anion is always larger than atom from which it is

formed.
Cations
• Positive ions are smaller than the atoms they
come from. Sodium is 2,8,1; Na+ is 2,8. You've
lost a whole layer of electrons, and the
remaining 10 electrons are being pulled in by the
full force of 11 protons. Also, an increase in Z eff.

Anions
• Negative ions are bigger than the atoms they
come from. Chlorine is 2,8,7; Cl- is 2,8,8.
Although the electrons are still all in the 3-level,
the extra repulsion produced by the incoming
electron causes the atom to expand. There are
still only 17 protons, but they are now having to
hold 18 electrons. Also, a decrease in Z eff.
The Radii (in pm) of Ions of Familiar Elements
Comparison of Atomic Radii with Ionic Radii
Ionization energy is the minimum energy (kJ/mol) required to
remove an electron from a gaseous atom in its ground state.

I1 + X (g) X+(g) + e- I1 first ionization energy

I2 + X+(g) X2+(g) + e- I2 second ionization energy

I3 + X2+(g) X3+(g) + e- I3 third ionization energy

I1 < I2 < I3
Variation of the First Ionization Energy with Atomic Number
 General Trends in First Ionization Energies

Increasing First Ionization Energy

Increasing First Ionization Energy

20
Electron affinity is the negative of the energy change that occurs
when an electron is accepted by an atom in the gaseous state to
form an anion.

X (g) + e- X-(g)

F (g) + e- X-(g) H = -328 kJ/mol EA = +328 kJ/mol

O (g) + e- O-(g) H = -141 kJ/mol EA = +141 kJ/mol

Variation of Electron Affinity With Atomic Number
Electronegativity is the ability of an atom to attract toward
itself the electrons in a chemical bond.

Electron Affinity - measurable, Cl is highest

X (g) + e- X-(g)

Electronegativity - relative, F is highest

The Electronegativities of Common Elements
Polarizability, α is the ease with which the electron distribution in
the atom or molecule can be distorted.

Polarizability increases with:

• greater number of electrons
• more diffuse electron cloud

A polarizable atom or ion is one

with orbitals that lie close in
energy; large heavy atoms and
ions tend to be highly polarizable.

(a) Low electronegativity and polarizability

(b) High electronegativity and polarizability
Molecular Orbital Theory
The basics of MO theory…

Symmetry properties & relative energies of atomic orbitals

determine how they interact to form MOs.

MOs are the occupied by electrons – same rules for atomic

orbitals.

If total energy of electrons in MOs < total energy of

electrons in atomic orbitals, then molecule is stable
compared to separate atoms. If not, the molecule doesn’t
exist.
Wave-like electrons

Modelling of a MO from atomic orbitals is called “linear

combination of atomic orbitals (LCAO)” – sums and differences
of atomic wave functions,Ψ.

What gives
Gives Gives
nonbonding
bonding antibonding
orbital & where
orbital orbital
does it appear?

antibonding
Coefficient
Ψ-

MOs of H2 : Ψ± = caΨa ± cbΨb Ψa Ψb

Molecular wave Atomic wave Ψ+

function function
bonding
 3 conditions for overlap that lead to bonding:

• Symmetry of orbitals where regions with same sign of Ψ

overlap.

• Energies of atomic orbitals must be similar.

• Distance between atoms must be short enough to provide

good overlap.
Particle-like electrons

Overlap is positive (bonding) when the superimposed

region are of same symmetry and the two orbitals have
the same signs.
Particle-like electrons

Overlap is negative (antibonding) when the superimposed

regions are of same symmetry and the two orbitals have
opposite signs.
Particle-like electrons

Overlap is zero when there are no overlaps and the

superimposed regions are of nonsymmetriy.
Molecular orbitals from s orbitals
Molecular orbitals from p orbitals

(a) Formation of MOs.

(b) Orbitals that do not form MOs.
Energy level diagram for
O2 and F2. (c) Energy level diagram
 A bonding σ orbital is g.
An antibonding σ orbital is u.

σ interactions

A bonding π orbital is u.
An antibonding π orbital is g.

π interaction
(a) Bonding
(b) Antibonding
Variation of orbital energies for period 2 homonuclear diatomic molecules
Energy level diagram for Energy level diagram for
O2 and F2. molecules from Li2 to N2.
In addition to symmetry, forming MOs depends on relative energy
of the atomic orbitals.

When atomic orbitals have same energy, interaction is strong.

When atomic orbitals have different energies, interaction is

weaker and resulting MOs have energies and shapes closer
to atomic orbitals.
Molecular orbitals
from d orbitals

(a) Formation of MOs.

(b) Orbitals that do not form MOs.
 Heteronuclear molecular orbitals

Heteronuclear diatomic molecules are polar.

Bonding electrons tend to be found

on the more electronegative atom
and antibonding electrons on the
less electronegative atom.
 Hydrogen fluoridec
5 atomic orbitals form 5 molecular
orbitals.

σ orbitals of HF are formed from

overlap of H1s with F2s and F2pz
orbitals. 3 atomic orbitals form 3 Mos.

F2px and F2py orbitals are unaffected

as they have π symmetry and H
orbital is not of that symmetry. These
π orbitals are nonbonding orbitals.

No centre of inversion in heteronuclear

diatomic molecule – do not use u and
g.
 Carbon monoxide
1σ orbital is localised mostly on O
atom and is bonding.

2σ orbital nonbonding.

1π orbital has doubly degenerate

pair of π bonding, mainly C2p
orbital character.

HOMO in CO is 3σ, predominantly

C2pz in character, largely
nonbonding & located on C atom.
LUMO is doubly degenerate pair of
antibonding π orbitals, mainly C2p
orbital character.
This combination of frontier orbitals (a full σ orbital largely localised
on C and a pair of empty π orbitals) – a reason why metal carbonyls
are such a characteristic feature of d-metals.
 Polyatomic molecular orbitals
More complex than diatomic.
Ψ = Σi ciΧi

N atomic orbitals contruct N mocular

orbitals:

Greater no. of nodes in MOs, greater

the antibonding character & higher
energy level.
Orbitals constructed from lower
energy atomic orbitals lie lower in
energy.
Interactions between nonnearest-
neighbour atoms are weakly bonding
and weakly antibonding.
UV photoelectron
spectrum of NH3.
 Ammonia

MOs to accommodate 8 valence

electrons in the molecule.

Each MO is combination of 7 atomic

orbitals; 3 H1s orbitals, N2s orbital &
3 N2p orbitals.

7 MOs constructed from 7 atomic

orbitals.

Notations σ & π not appropriate

because they apply to linear
molecules.
 Ammonia

a & b – nondegenerate orbital

e – doubly degenerate orbital (2
orbitals of same energy)
t – triply degenaret orbital (3 orbitals
of same energy)

Subscripts & superscripts are

sometimes added to a, b, e & t
such as a1, b”, eg & t2 (according to
more detailed analysis of their
symmetries).
 Ammonia
N2pz & N2s orbitals have cylindrical
symmetry about z axes.
Three H1s orbitals match the
cylindrical symetry about z axes.
Ψ = c1ΧN2s + c2ΧN2pz + c3 (ΧH1sA + ΧH1sB + ΧH1sC )

Resulting 3 orbitals are

nondegenerate – 1a1, 2a1 & 3a1

N2px & N2py orbitals have π symmetry

about z axes.
Two H1s orbitals match the π
symetry about z axes.
Ψ = c1ΧN2px + c2 (ΧH1sA + ΧH1sB)
Chemistry in action! (MO theory)
 UV-vis Spectroscopy
• Involves the spectroscopy of photons in the UV-visible
region.

•This means it uses light in the visible and near ultraviolet

and near infrared ranges.

•In this region of the electromagnetic spectrum, molecules

undergo electronic transitions.
Equation of Beer-Lambert law:

A = cx L x ε

A = absorbance of the sample, also defined below in terms of

light intensity

c = concentration of the absorbing species (in mol/ L unit)

L = path length traveled by the light beam through the sample

(in cm)

ε = molar extinction coefficient of the absorbing species (in mol -

1
cm-1L unit)
 Electronic transitions

Absorption of ultraviolet and visible radiation in organic molecules is

restricted to certain functional groups (chromophores) that contain
valence electrons of low excitation energy.

There are 3 types of electronic transition which can be considered:

a) Transitions involving π, σ, and n electrons

b) Transitions involving charge-transfer electrons
c) Transitions involving d and f electrons
Possible electronic transitions of π, σ, and n electrons are:
σ-σ* transition

An electron in a bonding s orbital is excited to the corresponding antibonding orbital.

The energy required is large.

For example, methane (which has only C-H bonds, and can only undergo σ-σ*
transitions) shows an absorbance maximum at 125 nm.

Absorption maxima due to σ-σ* transitions are not seen in typical UV-vis spectra
(200 - 700 nm).

n-σ* transition

Saturated compounds containing atoms with lone pairs (non-bonding electrons)

are capable of n-σ* transitions.

These transitions usually need less energy than σ-σ* transitions.

They can be initiated by light whose wavelength is in the range 150 - 250 nm.

The number of organic molecules with n-σ* peaks in the UV region is small.
n → π* and π → π* transitions

Absorption peaks for these transitions fall in an experimentally convenient region of

the spectrum (200 - 700 nm).

ε for n → π* transitions are relatively low (10 -100 L mol-1 cm-1 ).

ε for π → π* transitions are higher (1000 -10000 L mol-1 cm-1 ).

The solvent in which the absorbing species is dissolved also has an effect on the
spectrum of the species.

Peaks resulting from n → π* transitions are shifted to shorter wavelengths (blue shift)
with increasing solvent polarity. This arises from increased solvation of the lone pair,
which lowers the energy of the n orbital.

Often (but not always), the reverse (i.e. red shift) is seen for π → π* transitions. This
is caused by attractive polarisation forces between the solvent and the absorber,
which lower the energy levels of both the excited and unexcited states.
Charge transfer transition

Many inorganic species show charge-transfer absorption and are called charge-
transfer complexes.

For a complex to demonstrate charge-transfer behaviour, one of its components

must have electron donating properties and another component must be able to
accept electrons.

Absorption of radiation then involves the transfer of an electron from the donor to an
orbital associated with the acceptor.

ε for charge-transfer absorption (1000- >10000 L mol-1 cm-1) at λmax > 400 nm.
 Charge Transfer (CT)
O O

N R N R

O +
Fc O -
Fc

e*1u

a*2u
a*1g

e*2g
e2g,e2u e*2u
4p
e*1g
(dxz, dyz)
4s

a'1g
(dz2) Empty π* of acceptor
3d
e2g
e1g,e1u (dx2-y2, dxy)

e1u
e1g
a1g,a2u
a2u
a1g

Types of CT – MLCT, LMCT & MVCT

(Cp)2 Fe(C5H5)2 Fe
 UV-vis Spectra
Concentration = ?
Path length = ?
Absorbance = ?
1.0 Calculate the ε

0.8
Absorbance

0.6 A= 0.42 at 440 nm

0.4

0.2

0
250 300 350 400 450 500 550 600
Nanometers
 UV Spectra
Question: To prepare a sample, 0.03 mg of the compound below is
dissolved in 5 mL of dichloromethane solvent. Calculate the ε and
1.0 determine the electronic transitions involved for bands A and B.
(FW for the compound below is 423.29)
O

N CH3
0.8
O

Fe
0.6
Absorbance

A = 0.28, λmax= 330

0.4
A = 0.10, λmax= 480
0.2
A

0 B

300 400 500 600 700

Nanometers
Answer:

To determine the electronic transition:

a) λmax falls in the range of the transition
b) ε falls in the range of the transition

Band A at λmax= 330, ε = 19718 mol-1cm-1L (π- π*)

Band B at λmax= 480, ε = 7042 mol-1cm-1L (CT)
End of Topic 1