Chemical Bonding

MDM, 2011-2012
1
Department of Chemical Engineering
& Biotechnology

Part IA. Convergence

CHEMICAL BONDING
















Dr Mick Mantle
(mdm20@cam.ac.uk)


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Synopsis
1. Introduction
1.1 The Periodic Table
2. Valence bond theory
2.1. What is it?
2.2. Guidelines for drawing Lewis structures.
2.3. Valence shell electron pair repulsion (VSEPR) theory
2.4. Limitations of valence bond theory
3. Quantum mechanics in chemical bonding
3.1. Some general principles
3.1.1. Wave-particle duality
3.1.2. Heisenbergs uncertainty principle
3.1.3. Schrdinger equation
3.2. Atomic orbitals: one-electron atoms
3.2.1. Schrdinger equation
3.2.2. General features of wavefunctions
3.2.3. Energy level diagram for one-electron atoms
3.2.4. Shapes of atomic orbitals for one-electron atoms
3.3. Atomic orbitals: multi-electron atoms
3.4. Periodic trends in properties of atoms.
3.4.1. Example: 1
st
ionisation energy
3.4.2. Some comments on electronegativities
4. Molecular orbital theory
4.1. Linear Combination of Atomic Oritals (LCAO)
4.2. Formation of other molecular orbitals
4.3. Molecular orbital energy diagrams for homonuclear diatomic molecules
4.4. s-p mixing
4.5. Molecular orbital energy diagrams for heteronuclear diatomic molecules
4.6. Hybridisation of atomic orbitals
4.7. Three-centre two-electron bonds
4.8. Limitations of molecular orbital theory
5. Bonding in Solids
5.1. Types of solid
5.2. Molecular orbital theory for solids
5.3 Electrical Conductivity
5.3.1 Metals
5.3.2 Insulators
5.3.3 Intrinsic semi-conductors
5.3.4 Intrinsic semi-conductors
6. Transition Metal Chemistry
6.1. Oxidation numbers
6.2. Electronic configuration (18-electron rule)
6.3. Shape
6.4. Metal-Metal bonds
6.5. Cluster compounds
6.6. Metal-ligand bonding
6.7. Organometallic compounds


Recommended textbooks
- James Keeler & Peter Wothers Chemical Structure and reactivity OUP.
- P.W. Atkins Physical Chemistry. OUP.

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1 Introduction

You probably already know quite a lot about chemical bonding from what you learnt at
school. You probably have some idea about:


- The periodic table.
o Historically introduced as families of elements with similar properties.
o Periodic trends in the table are useful in predicting the properties of elements
and their compounds (e.g. trends in ionisation energy, electronegativity,
melting points of compounds).
o BUT have you ever asked yourself what is the theoretical basis for the
periodic table?


- Atomic orbitals.

o Provides a basis for the periodic table, by saying electrons fill up s
orbitals, p orbitals, d orbitals, f orbitals within each atom.

o There is independent experimental evidence for the existence of atomic
orbitals in addition to the mere fact of existence of the periodic table.
o BUT have you ever asked yourself about the theoretical basis for atomic
orbitals? Why do electrons around an atom arrange themselves in this way?


- Chemical bonding.
o You should have some idea about ionic bonding, typified by Na
+
Cl

.
o You should have some idea about covalent bonding, typified by ClCl.
o This school-level bonding model is called valence bond theory.
o It is a simple theory, and satisfactorily explains the bonding in many
compounds (including NaCl, Cl
2
, diamond, SiO
2
and virtually all organic
chemicals).

o BUT the properties of quite a lot of compounds cannot be explained
completely by valence bond theory.

These include some simple molecules (such as CO and O
2
), metals, and many
inorganic molecules (e.g. organometallic complexes and cluster compounds).



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The purpose of this course is to:

- Revise valence bond theory concepts (because theyre useful in many, though not all,
cases).


- Answer the question what is the theoretical basis for atomic orbitals and for the periodic
table.


- Introduce you to the molecular orbital theory of chemical bonding.


- Discuss the various types of bonding in solids (drawing on molecular orbital theory where
appropriate).


- Discuss the inorganic chemistry of transition-metal complexes (drawing on molecular
orbital theory where appropriate).

In addition to the formal lectures there will be an exercise sheet which seeks to provide
quantitative problems which illustrate the material covered.




Knowledge of the concepts taught in this course should be useful whenever you interact with
real chemists in the real world.

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1.1 THE PERIODIC TABLE

The Periodic Table

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2 Valence bond theory

2.1 What is it?

The key feature of valence bond theory is that it is a localised approach, in which
individual electrons can be recognised as being located either in a specific bond or
on a specific atom.

The number of Valence Electrons (VEs) in the outer shell of an atom is termed the valency of that
element, and it can be determined by inspection of the ground state electronic configurations of the
elements of the periodic table. (We shall discuss what precisely outer shell means when we
discuss quantum mechanics). As a rule of thumb to identify the number of valence electrons in an
atom we can use the following:

s-block : Use the superscripted number of last entry of the ground state electronic
configuration

Beryllium (Atomic number 4): VEs =

p and d-block : Use the summation of the TWO superscripted numbers of the ground
state electronic configuration ignoring any d
10
or f
14



Oxygen (Atomic number 8): [He] 2s
2
2p
4
` VEs =



Germanium (Atomic number 32): [Ar] 3d
10
4s
2
4p
2
VEs =



Iridium (Atomic Number 77): [Xe] 4f
14
5d
7
6s
2
VEs =


The square brackets around an individual element, i.e. [He] is a shorthand notation of the ground
state electronic configuration of that element.

There are generally two types of chemical bond:

(1) A covalent bond is formed when two atoms are held together by a pair of electrons which
are shared between the two atoms.





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(2) An ionic bond is formed when an electron is transferred from one atom to another. In
reality there never can be complete electron transfer, so a bond always has some covalent
character.





For both covalent and ionic bonding there is a propensity to attain the electronic configuration of the
nearest noble gas.

- Atoms from the early rows of the periodic table have a tendency to have 8 electrons in their
outer valence shells. This is the so-called octet rule; however, it should be viewed as a
guideline rather than a rule.

- Main-group atoms from latter rows of the periodic table have a tendency to have 18 electrons in
their outer valence shells if the d orbital electrons are counted (or 8 electrons if the d orbital
electrons are not counted).


- Transition metal atoms sometimes have a tendency to have 18 electrons we
shall consider this in more detail later in the course.



For covalent bonds, the number of bonding pairs of electrons is termed the bond order. Thus Cl
2
has
a single bond, O
2
a double bond, and N
2
a triple bond. These bonds are commonly represented by:

Cl
2
O
2
N
2







Covalent bonds will be polar if the bonded atoms have different electronegativities (a measure of
the power of an atom in a molecule to attract electrons). Polar bonds are expected to have some
degree of ionic character (e.g.
+
HF

).










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Pairs of electrons not involved in bonding are termed lone pairs (l.p.) or non-bonding pairs (n.b.p)
(e.g., water H
2
O and ammonia H
3
N).












Species with unpaired electrons are called radicals. They are often, but not always, reactive species.











There are only a few exceptions to the noble gas configuration rule for the elements in the early
rows of the periodic table.


- Examples of electron deficient species are BF
3
and AlCl
3
. Electron deficient compounds are
sometimes termed Lewis acids as they can readily accept a pair of electrons from another atom
to form a dative bond, e.g. H
3
NBF
3
(in which all atoms have now achieved noble gas
configurations). Note that, once formed, dative bonds are indistinguishable from normal
covalent bonds.












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- For elements in the third row of the periodic table there are examples where the number of
outermost electrons around the elements exceeds that of the nearest noble gas, e.g. PCl
5
and SF
6
.
These are sometimes termed hypervalent species. They are traditionally explained as being
due to the involvement of d orbitals in the bonding (which cant occur for second row elements).










Some structures cannot be adequately represented by a single diagram showing the pattern of bonds
in the molecule, as they exist as a resonance hybrid of different contributing structures. Well-
known examples include benzene (in which all bond lengths are equivalent) and the CH
3
COO

(acetate/ethanoate) anion. In some cases the contributing resonance structures can have quite
different electronic structures and energies, e.g. the cyanate anion:

NCO

N=C=O.








BUT BENZENE (C
6
H
6
)











- in valence bond theory diagrams, each line is a PAI R of
electrons.

- all electrons are indistinguishable from each other (i.e. it is impossible to state whether a
particular electron originated from one atom or another).

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2.2 Guidelines for drawing Lewis Structures

Example: Carbonate Ion: CO
3
2-


(i) Count total number of valence electrons in molecule to be formed. (For [XX]
-
or [YY]
+
ions
subtract / appropriate amount of electrons.


#ATOMS Additional
charge
on
molecule
Total Electron
count
( #v.e.)
Carbon

Oxygen
Number of
valence
electrons
(# v.e)





(ii) Connect atoms with single bond initially using LEAST electronegative (see page 44) atom as
central atom










(iii) Complete OCTETS around MOST electronegative atom













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(iv) Place surplus electrons on central atom (even if it means more than OCTET..??hypervalent??).




(v) If central atom still not OCTET, donate non-bonding pair into bond.














(vi) If molecule has an overall negative charge put this on most electronegative atom(s), but
remember there may be resonance structures



ALSO, REMEMBER SYMMETRY, i.e. N
2
O (Nitrous oxide, laughing gas)

NNO VS. NON






LEWIS STRUCTURES:

- Provides information about atom connectivities
- Provides information about valence orbitals: bonding/non-bonding
- Provides information about bond character, i.e. single, double, resonance structures.

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Examples:

Describe using valence bond theory the Lewis structure of:


(a) Hydroxide Ion [OH]
-

Guideline (i)

#ATOMS Additional
overall charge
On molecule
Total
Electron
count (
#v.e.)
Hydrogen

Oxygen
#
(v.e)




Guidelines (ii & iii)












Guideline (vi)










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(b) Carbon Monoxide (CO)
Guideline (i)

#ATOMS Additional
Charge
On
molecule
Total
Electron
count
Carbon

Oxygen
# (v.e)



Guidelines (ii & iii)












Guideline (v)










Guideline (vi)










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(b) Trifluorochlorine ( ClF
3
)
Guideline (i)

#ATOMS Additional
Charge
On
molecule
Total
Electron
count
Chlorine

Fluorine
# (v.e)



Guidelines (ii & iii)












Guideline (iv)






















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2.3 Valence Shell Electron Pair Repulsion (VSEPR) theory

This is a method of predicting the shapes of molecules based on valence bond theory. It assumes
that the geometry of molecules is based on electron-electron repulsion. It works extremely well for
main-group elements. However, it isnt applicable to transition metal or lanthanide complexes (see
later in course). VSEPR theory is based on the following assumptions:

- Bonds between atoms in a molecule consist of electron pairs.





- Some atoms may possess lone pairs (i.e. non-bonded pairs).







- Electron pairs adopt positions to minimise their mutual repulsion. The justification for this is
that areas of negative charge density repel other regions of negative charge density.


- Lone pairs (lp) repel more than bonding electron pairs (bp),
i.e. repulsion is in order





- If more than one possible structure exists we have to consider different geometrical
arrangements, BUT keep to the Basic geometric arrangement of electon pairs described in the
table below!. Make a table of interactions and ONLY CONSIDER ELECTRON PAIR
INTERACTIONS AT RIGHT ANGLES, i.e. 90 degrees to EACH OTHER









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- Multiple bonds are treated as though they were a single electron pair for geometric purposes;
this means that the basic coordination geometry is dictated by the bonding framework only.
Multiple bonds will, however, occupy more space than single bonds.


The basic Geometric arrangement of electron pairs around the central atom will be








































Electron
pairs
Geometry Molecule
2 Linear AX
2

3 Trigonal planar AX
3

4 Tetrahedral AX
4

5 Trigonal bipyramid
(common)
Square-based
pyramid (rare)
AX
5

6 Octahedral AX
6


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When doing problems:
- Count valence electrons + draw Lewis structure
- Remember to bear in mind the charge on the complex if any
- Determine the number of electron pairs present & remember the rule that repulsion is :


> >

- Use Table of basic geometric arrangements as starting point for structure

- If more than one possible arrangement of electron pairs exists, make a table of lp/lp, lp/bp and
bp/bp interactions and CONSIDER ONLY ELECTRON PAIR INTERACTIONS AT RIGHT
ANGLES, i.e. 90 degrees to EACH OTHER

Note that while bonds dont directly affect the choice of molecular shape, they do need to be
considered for electron counting purposes!





Examples

H
2
O

#v.e. Lewis
Structure
# e
-
pairs Basic
Structure
Repulsion Approx
Bond Angle



















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NH
3


#v.e. Lewis
Structure
# e
-
pairs Basic
Structure
Repulsion Bond Angle
















NH
4
+


#v.e. Lewis
Structure
# e
-
pairs Basic
Structure
Repulsion Bond Angle





















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ClF
3


#v.e. Lewis
Structure
# e
-
pairs Basic
Structure
Repulsion Bond Angle













BUT OTHER ARRANGEMENTS POSSIBLE








Structure
lp/lp lp/bp bp/bp
(a)
(b)
(c)

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2.4 Limitations of valence bond theory

Valence bond theory, as described above, is simple and it is often an adequate description of
chemical bonding. However, it fails to explain the bonding in some molecules. For instance:

- Why is O
2
attracted to a magnet, implying that it must possess one or more
unpaired electrons?

- Why does CO bind to metals through the carbon atom, i.e. behave as

CO
+
in contrast to
what would be expected on simple electronegativity grounds?



- What is the bonding like in the molecule B
2
H
6
, in which two of the hydrogen atoms bridge the
boron atoms?




- What is the bonding like in Zeises salt, K [Pt(C
2
H
4
)Cl
3
] .H
2
O? This was first made in 1827, but
it wasnt established unambiguously until the 1950s that ethene is bonded to the platinum atom.




- What is the bonding like in ferrocene, Fe(C
6
H
6
)
2
, in which the iron atom is equidistant to all the
carbon atoms?




- What is the bonding like in the [Re
2
Cl
8
]
2
anion, in which the ReRe distance is only 2.24 (far
closer than the atoms are in rhenium metal), and the chlorine atoms adopt a configuration in
which they sterically hinder each other?



Valence bond theory also fails to provide any information on the ease with which an electron can be
removed from a molecule, or alternatively the energy change if an electron is added to a molecule.

For all these questions, we need another bonding theory that takes into account more features of
quantum mechanics.

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3 Quantum mechanics in chemical bonding

3.1 Some general principles

All of chemical bonding ultimately depend on quantum mechanics. The proof that quantum
mechanics is a good theory is that it works and has never yet failed (unlike classical mechanics
which only works for big systems). We dont have time to go properly into quantum mechanics,
and so all were going to do in this course is to use a few key points without any justification (sorry,
while its a really interesting subject, its not directly relevant to chemical engineering).

3.1.1 Wave-particle duality

Things that we normally associate as being particles have wave-like properties, while things we
normally associate as being waves have particle-like properties. Two important examples:

- Light (electromagnetic radiation) of frequency consists of photons, each of
energy

E = h (Planck equation)

where h = Plancks constant (6.626 x 10
34
J s).

For instance, light behaves as particles in the photoelectric effect.















- When light behaves as a particle is has an associated kinetic energy T given by:







As intensity of light ,
number of photoelectrons

BUT the K.E. of

photoelectrons does not
change
Red light does not cause
electrons to be ejected
whatever the intensity
Only when light is of
sufficient energy will it
cause the ejection of
electrons from the surface

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- But de Broglie suggested that particles with momentum p have an associated
wavelength



This is demonstrated by experiments such as the diffraction of light (as electrons)


























- Using de Broglies relationship it is possible to express the Classical General
Wave Equation as:








The classic general wave equation tells us how a system evolves according to Newtons
Laws.
LIGHT SOURCE LIGHT SOURCE

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3.1.2 Heisenbergs uncertainty principle

This states that it is not possible to know simultaneously the position and
momentum of a particle.

While classically unintuitive, it follows from the fact that a particle that is nominally at rest at a
single point must still be behaving like a wave (in some fashion) it must have some oscillation in
position and/or momentum.

In quantitative terms, it can be shown that the product of the uncertainties always obeys:

p x /2 where = h/2

An equivalent statement is E t /2, where t is the uncertainty in the time that the particle
spends in an energy level that has uncertainty E.

Because of the Heisenberg uncertainty principle, we are no longer able to talk about the position of
a particle such as an electron.

I nstead, we can only talk about the probability of finding the
particle in a specified volume.

3.1.3 Schrdinger Equation....(The equation of motion of waves!)
The Schrdinger equation is the quantum mechanical equivalent of the general wave equation given
back on the previous page. The Schrdinger equation describes how a quantum state, which we call
the WAVEFUNCTION {(x,y,z,t)}, evolves in time and space. The wavefunction, , is a
(quantum) mathematical description of where a particle is in space. The Schrdinger equation is
completely deterministic and may have many solutions for a given wavefunction (Schrdingers
Cat!!). However in order to know something about the wavefunction we must somehow measure it.
Mathematically, we do this by collapsing the wavefunction and thus convert the wavefunction into a
PROBABILITY distribution of finding a particle in a volume element dV. The probability is given
by
2
dV. (More rigorously, the probability function is
*
dV where the asterisk denotes
complex conjugate). The time-independent Schrdinger wave equation for a particle of mass, m,
experiencing a potential energy, V(x, y, z) is:



E V
m
= +
|
|
.
|

\
|
c
c
+
c
c
+
c
c
2
2
2
2
2
2 2
2
z y x

where E is the energy of the system.


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For a system changing with time the time-dependent form of the equation is:

t
i
z y x
c
c
= +
|
|
.
|

\
|
c
c
+
c
c
+
c
c

V
m
2
2
2
2
2
2 2
2


where i is the square root of 1.

We can now define a system by specifying the potential energy function V, specifying the boundary
conditions and then attempt to solve this equation. It turns out that the time-independent equation
can be solved exactly only in very simple cases. One of these, usually termed the particle in a box,
is on your examples sheet. Another that can be solved exactly is the hydrogen atom we shall
discuss this in a little while.

In those simple cases where we can solve the Schrdinger equation, we discover that:


- The equation may only be solved if the energy E of the system takes certain
values there are no solutions for other E values. Thus the concept of
quantisation of energy is in fact a direct consequence of nature obeying the
Schrdinger equation.

- We characterise the solutions by quantum numbers these are parameters that can
only take certain values. For instance, the solution to a particle in a box (see examples sheet)
implies that the only permitted values of E are n
2

2
/2ma
2
(where m is the particle mass and a
is the length of the box). Here n is a quantum number that takes values 1, 2, 3, 4, etc.

- Each solution gives us an expression for the wavefunction for the system
with that particular energy.

- Each solution has a particular probability function for the location of the
particle in a given volume dV.


- I n order for the total probability to sum to unity, we must normalise the
wavefunction so that:






It turns out that these rules also hold for the more complicated cases in which we cannot solve the
Schrdinger equation exactly. In these cases, we can still obtain approximate solutions using
computing methods.

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Solving the Schrdinger wave equation for a free particle moving in one
dimension in a constant potential V
0



(i) Write down the time independent Hamiltonian operator




(ii) Write down the Eigenvalue (Scrodinger) equation and rearrange.







(iii) Consider the case where E > V
0
, i.e. (E-V
0
) is positive. Remember kinetic
energy is never negative in classical mechanics. To solve (1) we GUESS the
solution!






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(iv) Substitute the guess in (iii) into the equation you obtained in (ii) & then
evaluate














(v) Equate RHS of equation 1 with RHS of equation (2) in (iv)










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GRAPHICAL REPRESENTATION OF PREVIOUS EQUATION
























- Free particle moves/oscillates with increasing energy
BUT
- This solution is NOT Quantised or Normalised

- MUST impose Boundary Conditions to complete
quantisation





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3.2 Atomic orbitals: one-electron atoms

We shall initially discuss the case of atoms containing only one electron (i.e. H,
He
+
, Li
2+
etc.), as the Schrdinger equation can be solved exactly in this case.

3.2.1 Schrdinger equation

In this case the potential energy function is the Coulombic energy, and the time-independent
Schrdinger equation is:


tc

E
Ze
=
|
|
.
|

\
|
c
c
+
c
c
+
c
c
2
0
2
2
2
2
2
2
2 2
1
4 2
r z y x

where Z is the atomic number, e the charge of an electron, r is the separation of electron and
nucleus, and is the reduced mass (given by 1/ = 1/m
electron
+ 1/m
nucleus
). Use of the reduced mass
allows for the fact that the nucleus as well as the electron will be moving. The Schrdinger equation
can then be transformed from Cartesian coordinates (x, y, z) into spherical polar coordinates (r, ,
), and solved. The boundary conditions necessary to ensure that the wavefunction gives a
meaningful probability density are:

must be single-valued in space








must vary smoothly and
cannot suddenly jump from one value to another








The integral of * over all space
and must be finite






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The solutions for the wavefunction depend on three quantum numbers, normally designated n, l and
m
l
, and the solutions can be written in the form:


= R(n, l, r) Y(l, m
l
, , )



The solutions thus contain two separate parts:

- a radial part (giving the r dependence) this depends only on n and l quantum numbers
- and an angular part (giving the , dependence) this depends only on l and m
l
quantum
numbers.

It turns out that the functions R(n, l, r) and Y(l, m
l
, , ) had been discovered before Schrdinger
was born as they are solutions to interesting differential equations that had been previously
studied. The functions are known as associated Laguerre polynomials and spherical harmonics,
respectively (you dont need to remember these names!).

The lowest energy solutions have the following form (no need to remember these expressions):

n l m
l
Wavefunction Atomic orbital

1 0 0 = (1/) (1/a
o
)
3/2
exp(r/a
o
)

2 0 0 = (1/42) (1/a
o
)
3/2
(2 r/a
o
) exp(r/2a
o
)

2 1 0

= (1/42) (1/a
o
)
3/2
(r/a
o
) exp(r/2a
o
) cos

2 1 1

= (1/42) (1/a
o
)
3/2
(r/a
o
) exp(r/2a
o
) sin cos



= (1/42) (1/a
o
)
3/2
(r/a
o
) exp(r/2a
o
) sin sin

3 0 0 = (1/183) (1/a
o
)
3/2
(6 6r/a
o
+ r
2
/a
o
2
) exp(r/3a
o
)

[ a
o
is a constant termed the Bohr radius and is given by 4
o

2
/m
e
e
2
= 5.292 x10
11
m ]

These solutions have different energies, and different probability functions for the
electron location.

The solutions are more commonly called atomic orbitals, and denoted 1s, 2s, 2p,
3s, 3p, 3d etc. Hence we have discovered that atomic orbitals are simply solutions
to the Schrdinger equation for one-electron atoms.





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We now need to consider the physical significance of the quantum numbers.

- The principle quantum number 'n' (determines the ENERGY of the orbital)

o Has integral values of 1, 2, 3, etc.
o As n increases the electron density is further away from the nucleus
o As n increases the electron has a higher energy and is less tightly bound to the
nucleus:











- The orbital (azimuthal ;second) quantum number 'l ' (determines the type of orbital)

o Has integral values from 0 to (n-1) for each value of n
o Instead of being listed as a numerical value, typically ' l ' is referred to by a letter
('s'=0, 'p'=1, 'd'=2, 'f'=3)
o Defines the shape of the orbital; shading indicates a different phase
o Magnitude is l(l+1)





















( )
2 2
0 0
2 2
1
4 2 n n a
e Z

=
tc
E

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- The magnetic (third) quantum number 'm
l
' (determines orbital orientation)
o Has integral values between 'l' and -'l', including 0
o Describes the orientation of the orbital in space












- The spin quantum number 'm
s
'
o Further detailed analysis reveals that a fourth quantum number becomes necessary
when relativity is taken into account as well as simple quantum mechanics. This
quantum number is termed the electron spin quantum number m
s
, and it can take
values + and only.







Thus we have discovered that for one-electron atoms there is:

- One 1s orbital

- One 2s orbital, and three 2p orbitals of the same energy


- One 3s orbital, three 3p orbitals, and five 3d orbitals of the same energy

- One 4s orbital, three 4p orbitals, five 4d orbitals, and seven 4f orbitals of the same energy



Atomic orbitals that have the same energy
as each other are termed degenerate.






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32
3.2.2 General features of WAVEFUNCTIONS, (r, u, |) for one electron atom

The wavefunction (r, u, |,) is a mathematical description of the electron in space

By calculating * (remember * is the complex conjugate of ) at some point (r, u,
|) in space we determine the entirely real and thus measurable PROBABI LTI Y DENSI TY
for the electron AT THAT POINT.

(r) is a RADIAL wavefunction function; it is real and makes a contribution to the total
probability density function of
2
(r). (its unit is 1/Volume and hence this is why it is
thought of as a density functionmultiplication of this density function by a infinitesimal
volume of space, dt=dxdydz, gives the occupation number in a small element of space).
Note: in general (r) does not give a true indication of the electron distribution in an
orbital since it only represents part of the wavefunction


Integration of the occupation number, i.e. sum of various probabilities for each infinitesimal
volume element dt over all space gives the total occupation of the electron in all space,
which must equal unity, i.e.






Conversion of dt from Cartesian to Spherical polar coordinates gives:






The TOTAL probability density function is a product of both the square the RADIAL
FUNCTION, which having been converted to spherical polar coordinates, we now denote
R
2
(r), and the square of the ANGULAR FUNCTION Y*Y(l, m
l
, , f)













1 , ( * = ) ,
}
space all
d r t | u
| u u t d d dr r d sin
2
=
( ) ( ) ( ) | u u | u | u
t t
d d Y Y dr r r R sin , ,
0 0
2
0
* 2 2
} } }

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33
NOTE: R
2
(r) is a probability (per unit volume) density function for the DISTANCE of the
electron from the nucleus EXCLUSIVE of any ANGULAR variation. It is more intuitive,
when thinking about the probability where electrons are in space, to think about the
probability of finding an electron in a thin shell of radius r and thickness dr.


The reason this approach is particularly useful is that it adds up the probability of finding an
electron in all spatial directions and thus give us a measure of the probability of finding
an electron at a particular DISTANCE from the nucleus, regardless of direction.

The surface density function(SDF) is defined by:

SDF = 4t r
2
R
2
(r) P(r)

and takes into account explicit angular variation. The SDF is equivalent to P(r), the
RADIAL DISTRIBUTION FUNCTION (RDF).


The product of the SDF/RDF with the thickness of the thin shell, i.e.

P(r) dr =4t r
2
R
2
(r) dr

is then defined as the probability of finding the electron in a shell of radius r and thickness
dr.




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34

r(a
0
) 2 4 6 8 10
4
t
R
2
(
r
)

r
2
,

(
1
/
a
0
)
Graphical sketches of hydrogen radial wavefunctions
(no inclusion of spherical harmonic, Y(l, m
l
, , |) )
1s surfacedensity function, 4tR
2
(r)r
2
Also known as the radial distribution/probability function RDF/RPF
1s radial function, R(r)
r(a
0
)
2 4 6 8 10
R
(
r
)
,

(
1
/
a
0
3
/
2
)
1s radial function, R(r)
r(a
0
)
2 4 6 8 10
R
(
r
)
,

(
1
/
a
0
3
/
2
)
1s radial probability
densityfunction R
2
(r) for
a given set of coordinates
r(a
0
)
2 4 6 8 10
R
2
(
r
)
,

(
1
/
a
0
3
)
1s radial probability
densityfunction R
2
(r) for
a given set of coordinates
r(a
0
)
2 4 6 8 10
R
2
(
r
)
,

(
1
/
a
0
3
)

1s
= R(r) = 2 (1/a
o
)
3/2
exp(r/a
o
)

Chemical Bonding
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35

0
0 5 10 15
0
0 5 10 15
Other radial distribution functions
Points to note:
1s electrons are on average a lot closer to the nucleus than electrons in higher orbitals
(you can show that the most likely distance = a
0
for 1s case).
There is a radial node in the probability distribution function of the 2s orbital. While the
2s and 2p orbitals are identical in energy for the hydrogen atom, there is a far higher
chance of a 2s electron being very close to the nucleus than for a 2p electron.
No. of Radial Nodes = (n - l - 1)
r(a
0
)
1s
2s
2p
Node
4
t
R
2
(
r
)

r
2
,

(
1
/
a
0
)

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36
3.2.3 Energy level diagram for one-electron atoms


Energy
n =
l = 0 l = 1 l = 2
n = 3
n = 2
n = 1
Ground state is lowest energy configuration
All systems try to adopt the lowest possible energy
One e
-
atoms occupies 1s orbital
Transistions (absorption/emission) to other orbitals
possible (hv ; k
B
T)

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37
3.2.4 Shapes of atomic orbitals for one-electron atoms




The combined radial ( R ( n , l , r ) ) and angular ( Y ( l , m
l
, , | ) ) wave functions give
rise to 3D electron ORBITALS. Below are isosurface representations of these for a particular
value of the wavefunction. !!NOTE the value of the iso-surface gives the apparent size of the
orbital, it doesnt reflect the electron density!!
s - orbitals are spherically symmetric
Higher s - orbitals have NODES where the electron density is zero
NO ANGULAR ( u , | ) PART for s - orbitals
r

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38
p - orbitals are dumbbell shaped
Node at the nucleus.
There are three distinct p - orbitals, they differ in their orientations
There is no fixed correlation between the three orientations and the three
magnetic quantum numbers (m
l
)
Combined radial (r) and angular ( u , | ) part

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d - orbitals have following shape
UNDERSTANDING ORBITAL SHAPES IS KEY TO UNDERSTANDING
THE MOLECULES FORMED BY COMBINING ATOMS
r

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40

Some useful concepts

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41
3.3 Atomic orbitals: multi-electron atoms

For atoms containing more than one electron the Schrdinger equation is far more complicated as
interelectron repulsion needs to be included in the potential energy function. It turns out that even
with only two electrons present the equation becomes too complicated to solve exactly! Theoretical
chemists can, however, get very close to the solution using computing methods. Important results
from their work are:

The approximate shape of the orbitals is unchanged use same labelling scheme as for the
hydrogen atom.

- Energies now also depend on the l quantum number. Calculations show that:
E(2s) < E(2p) and E(3s) < E(3p) < E(3d) ~ E(4s)
i.e. the {2s, 2p} and {3s, 3p, 3d}energy levels are no longer degenerate with each other.

- This is precisely the situation that had been conjectured when explaining the form of the
periodic table, only now it has been given a sound theoretical basis.

This arrangement of atomic orbital energy levels is normally rationalised at a qualitative level by
introducing the concept of electron shielding. Electrons in outer orbitals are shielded or
screened to a large extent from the full nuclear charge by the inner electrons due to interelectron
repulsion. Examination of the radial probability distribution plots for the hydrogen atom shows that
2s electrons are better able to penetrate close to the nucleus than 2p electrons, and thus that 2s
electrons are less effectively shielded from the nucleus by electrons in the 1s orbital. (see page 35)


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42









































n l m
l
m
s

2p
x

2p
y

2p
z



n l m
l
m
s

1s


Multi-electron atoms energy level diagram
RULES FOR PLACING ELECTRONS INTO ENERGY LEVELS
Pauli Exclusion principle: no electron may have the same set of
quantum numbers (n, l , m
l
, m
s
)
Aufbauprinciple: lowest E levels fill first
Hund s Rule: degenerate levels parallel spin-pair first, then once
all orbitals have been used, they pair-up according to Pauli.
Energy
1s
2s
2p
x
2p
y
2p
z
3s
3p
x
3p
y
3p
z
3d
1
3d
3
3d
4
3d
5
3d
2
n =
l = 0 l = 1 l = 2
n = 3
n = 2
n = 1
Energy
1s
2s
2p
x
2p
y
2p
z
2p
x
2p
y
2p
z
3s
3p
x
3p
y
3p
z
3p
x
3p
y
3p
z
3d
1
3d
3
3d
4
3d
5
3d
2
3d
1
3d
3
3d
4
3d
5
3d
2
n =
l = 0 l = 1 l = 2
n = 3
n = 2
n = 1

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43
This leads to the following ground state configuration of the elements:

1 H 1s
1
19 K [Ar]4s
1

2 He 1s
2
20 Ca [Ar]4s
2

3 Li [He]2s
1
21 Sc [Ar]4s
2
3d
1

4 Be [He]2s
2
22 Ti [Ar]4s
2
3d
2

5 B [He]2s
2
2p
1
23 V [Ar]4s
2
3d
3

6 C [He]2s
2
2p
2
24 Cr [Ar]4s
1
3d
5
(*)
7 N [He]2s
2
2p
3
25 Mn [Ar]4s
2
3d
5

8 O [He]2s
2
2p
4
26 Fe [Ar]4s
2
3d
6

9 F [He]2s
2
2p
5
27 Co [Ar]4s
2
3d
7

10 Ne [He]2s
2
2p
6
28 Ni [Ar]4s
2
3d
8

11 Na [Ne]3s
1
29 Cu [Ar]4s
1
3d
10
(*)
12 Mg [Ne]3s
2
30 Zn [Ar]4s
2
3d
10

13 Al [Ne]3s
2
3p
1
31 Ga [Ar]4s
2
3d
10
4p
1

14 Si [Ne]3s
2
3p
2
32 Ge [Ar]4s
2
3d
10
4p
2

15 P [Ne]3s
2
3p
3
33 As [Ar]4s
2
3d
10
4p
3

16 S [Ne]3s
2
3p
4
34 Se [Ar]4s
2
3d
10
4p
4

17 Cl [Ne]3s
2
3p
5
35 Br [Ar]4s
2
3d
10
4p
5

18 Ar [Ne]3s
2
3p
6
36 Kr [Ar]4s
2
3d
10
4p
6


This electronic structure is important as the outer (valence) electrons largely determine the
chemistry (in both valence bond theory and molecular orbital theory).

There is excellent direct experimental evidence for atomic orbitals and the ordering of their energy
levels from spectroscopy. If an atom is in an excited state, then it can fall down to a lower quantum
level by emitting a photon of frequency determined by the separation of the energy levels.
Measurements of the discrete frequencies emitted thus allows the separation of energy levels to be
determined experimentally.

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3.4 Periodic trends in properties of atoms

There are a number of periodic trends in the properties of elements across and down the periodic
table. These include ionisation energy, electron affinity, electronegativity and atomic radii. Most of
these can be easily rationalised using our knowledge of atomic orbitals.

3.4.1 Example: 1
st
ionisation energy

The 1
st
ionisation energy is the energy required to remove an electron from the neutral atom in the
gas phase:
0
10
20
30
0 10 20 30 40 50 60
Atomic number
1
s
t

i
o
n
i
s
a
t
i
o
n

e
n
e
r
g
y

(
e
V
)

The electron removed will come from the highest occupied energy level. Thus ionisation energy will
depend on the highest filled atomic orbital, the atomic charge and the electron shielding.The
periodic trends in 1
st
ionisation energy can be rationalised on this basis.

1. The large increase in I.E. across period (n is the same) because effective nuclear charge is
increasing. Each additional nuclear charge is having a greater effect than the extra electron
shielding.

2. There is a decrease in I.E. down a group. The electron is being removed from an atomic
orbital with higher n quantum number.

3. Certain deviations in this overall pattern occur:
a) Be (2s
2
) has a higher I.E. than B (2s
2
2p
1
): easier to remove 2p than from a full 2s level.
b) N (2s
2
2p
3
) has a higher I.E. than O (2s
2
2p
4
): there is extra stability associated with a
half-filled energy level (or, equivalently, there is an extra instability associated with
having to pair up an electron).

4. There is only a small increase in ionisation energy across transition metals effective
nuclear charge is increasing, but not outweighing the electron shielding term by as much as was the
He
Ne
Ar
Kr
Xe
Li Na
K Rb Cs
Zn
Ga In
Cd

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45
case for the main-group elements. This is because d (and f) orbitals are diffuse they do not
penetrate very close to the nucleus.

3.4.2 Some comments on electronegativity

Electronegativity is defined as the power of an atom I N A MOLECULE to attract
electrons. This means that electronegativities have no precise physical meaning. They cannot be
measured, and can vary for an element depending on which particular molecule it finds itself in.
Electronegativities predict that electrons are polarised towards electronegative atoms away from
electropositive atoms, and so are useful when discussing bond polarities. In most cases (but not all
cases), predictions based on electronegativities are correct.


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4 Molecular orbital theory

4.1 Linear Combination of Atomic Orbitals (LCAO) approach.
Solving the Schrdinger equation for one electron in a multi-atom system (i.e. a one-electron
molecule) in principle gives us a set of wavefunctions with energies E that correspond to
molecular orbitals by analogy to atomic orbitals. However, this is too complicated to do
rigorously. We thus have to make a simplifying assumption. Molecular orbitals (mo s) arise
from the overlap of atomic orbitals (ao s).
I .e.
mo
is derived from the LI NEAR COMBINATI ON OFATOMIC ORBITALS (LCAO),

mo
=
c
1

ao
1
+ c
2

ao
2
+ c
3

ao
3
...
Where c
i
represents the relative amounts contributed by the a.o. s
The simplest case: the H
2
+
molecule
Consider the H
2
+
molecule (i.e. two H nuclei, which we shall call A and B, and one single
electron).
In-phase linear combination of a.o wavefunctions
CONSTRUCTIVE overlap of two A.O. s give a single M.O. of lower energy, termed the
BONDING M.O.

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47

Anti - phase linear combination of a.o wavefunction
DESTRUCTIVE overlap of two A.O.s give a single M.O. of higher energy,
termed the ANTIBONDING M.O.
Combine in - phase and anti - phase combinations into a single energy level
diagram for H
2
+
Energy
1s 1s
Atomic
orbital
Atomic
orbital

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48
Note: the QM calculations show that the energy of the anti-bonding MO is raised slightly more in
energy, relative to the component AOs, than bonding MOs are lowered. However, this
behaviour is not always shown and often you will see no difference depicted in texts for simple
MO diagrams.
The way in which electrons are placed into MO s is exactly the same as that for the single and
multi-electron atom model discussed earlier (Pauli, Aufbau and Hund)
Some Examples
Energy
1s 1s
H
2
molecule
Energy
1s 1s
He
2
molecule?
He
2
moleculedoes not exist as it is unstable w.r.t He atoms

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The indicates that the molecular orbital has the same symmetry as an s atomic orbital - we use
greek letters for molecular orbitals. The subscript s indicates that these molecular orbitals arise
from s atomic orbitals, and the asterisk is used to indicate an antibonding orbital.

o and t molecular orbitals are numbered according to symmetry. DO NOT GET CONFUSED
WITH the quantum number label n


Electrons in bonding molecular orbitals have a lower energy as they are less constrained, i.e. more
delocalised, which means that is Kinetic Energy has decreased. The electron density is now shared
between two nuclei, which also results in a lowering in the energy of the system.

Electrons in anti-bonding orbitals have a higher energy due to the presence of a NODE/NODAL
PLANE


4.2 Formation of other molecular orbitals

The following general rules are obeyed:

1. Combining n atomic orbitals gives n molecular orbitals.

2. Only atomic orbitals of the correct symmetry will combine.

3. The energy of a molecular orbital relative to the atomic orbitals
from which it is derived depends on:
the relative energies of the atomic orbitals (close in energy
large interaction);
the degree of atomic orbital overlap between them (good overlap
large interaction).

4. Bond order = (#bonding electrons #antibonding electrons)


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There are two ways of combining p atomic orbitals, and these give different symmetry molecular
orbitals. Overlap of two p
z
orbitals end-on forms a bonding orbital. The sideways overlap of
two p
x
orbitals, and the sideways overlap of two p
y
orbitals form two bonding orbitals. (Note that
molecular orbitals have the same symmetry as p molecular orbitals). The resulting molecular
orbital shapes are shown below.

A
(s) +
B
(s)

A
(s)
B
(s)

A
(p
z
) +
B
(p
z
)

A
(p
z
) -
B
(p
z
)

A
(p
x
) +
B
(p
x
)

A
(p
x
) -
B
(p
x
)

A
(p
y
) +
B
(p
y
)

A
(p
y
) -
B
(p
y
)

A
(s) +
B
(s)

A
(s)
B
(s)

A
(p
z
) +
B
(p
z
)

A
(p
z
) -
B
(p
z
)

A
(p
x
) +
B
(p
x
)

A
(p
x
) -
B
(p
x
)

A
(p
y
) +
B
(p
y
)

A
(p
y
) -
B
(p
y
)
A.O.s A.O.s
M.O.s M.O.s

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51
In the normal case, the energy change on forming
p
molecular orbitals is less than that on
forming
p
molecular orbitals. We can thus draw an energy diagram showing the molecular orbitals
formed from the overlap of p atomic orbitals.







































We are now in a position to construct a molecular orbital energy level diagram for simple diatomic
molecules.




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52
4.3 Molecular orbital energy diagrams for homonuclear diatomic molecules

The molecular orbital energy diagram for O
2
and F
2
(and Ne
2
if it existed) can now be drawn, and is
shown below. Note that 1s 1s overlap will be negligible because electrons in the inner shell are too
close to one of the nuclei to interact with the other one and thus on the energy level diagram below
they would be way below the 2s atomic orbitals and remain as individual atomic orbitals. However,
the naming system still takes into account that the 1s atomic orbitals are there.

2p 2p
Energy
2s 2s
Atomic
orbital
Atomic
orbital
Molecular
orbitals

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53
4.4 s-p mixing

The situation for molecules Li
2
, Be
2
, B
2
, C
2
and N
2
is a little more complicated. It turns out that the
2s and 2p atomic orbitals are sufficiently close in energy that the 2s 2p
z
interaction is significant.
The 2s 2p
z
is a symmetry interaction and this, along with their close energy match, means that
the resulting molecular orbitals also have the same symmetry. It is then possible to take linear
combinations of the subsequent molecular orbitals of the correct symmetry in exactly the same way
as for atomic orbitals resulting in a shifting of the MOLECULAR ORBITAL energy levels. The
next two diagrams illustrate this process starting with the linear combination of MOLECULAR
ORBITALS which were originally formed from the linear combination of ATOMIC ORBITALS:


2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*

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54
Energy level diagram for s-p mixing.

NOTE DESPITE THE APPEARANCE ON THE DIAGRAM THAT
THE 2s and 2p ATOMIC ORBITALS ARE FAR APART IN ENERGY
THIS IS NOT THE CASE FOR Li
2
, Be
2
, B
2
, C
2
and N
2
AND IN
REALITY THEY ARE CLOSE ENOUGH TO ALLOW OVERLAP.




























NOTE: Whilst the 3o
p
and 3o
p
* have been raised in energy in the s-p
mixed case, this effect is outweighed by the lowering of the 2o
s
and 2o
s
*
orbitals
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*
2p 2p
3
p
3
p
*

p
*
2s 2s
2
s
2
s
*

Chemical Bonding
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55






































We thus have the following energy level diagrams for the homonuclear diatomic molecules from Li
2
to F
2
We can now write down the ground-state electronic configurations of the following homonuclear
molecules:
Li
2

s
2
Be
2

s
2

s
*
2
B
2

s
2

s
*
2

x
1

y
1
C
2

s
2

s
*
2

x
2

y
2
N
2

s
2

s
*
2

x
2

y
2

p
2
O
2

s
2

s
*
2

p
2

x
2

y
2

x
*
1

y
*
1
F
2

s
2

s
*
2

p
2

x
2

y
2

x
*
2

y
*
2
Ne
2

s
2

s
*
2

p
2

x
2

y
2

x
*
2

y
*
2

p
*
2
It can be seen that molecular orbital theory can successfully predict bond orders predict magnetic
properties. Molecules containing unpaired electrons are said to be paramagnetic; such molecules are
(fairly strongly) attracted by magnetic fields. Molecules in which all the electrons are paired are
termed diamagnetic; they are weakly repelled by magnetic fields.
Two key points:
A bond in MO theory results from electrons occupying molecular orbitals formed
from the favourable overlap of atomic orbitals of appropriate symmetry.
Much of the chemistry of molecules is determined by the properties of the Highest
Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), as
these are the orbitals that will be involved in any electron transfer processes.
Li
2
Be
2
B
2 C
2
N
2 O
2
F
2
E
n
e
r
g
y

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56

Naming system for molecular orbitals:

The naming system for molecular orbitals is not particularly logical and is usually based upon
symmetry operations/considerations. However with the exception of hydrogen, for homonuclear
diatomics of the second period row in the periodic table (which is all youll ever be asked about)
the bonding starts with the overlap of the 2s atomic orbitals. The two molecular orbitals that are
produced (one bonding and one anti-bonding) are named the 2o
s
and 2o
s
* respectively. Often for
simplicity the s subscript is dropped.









NOTE: that despite the physical existence of the 1s atomic orbitals in the second row elements,
these orbitals are too close to the nucleus to overlap and do not take part in bonding. The next most
favourable overlap for homonuclear diatomics of the second period (row) of the periodic table is
the sigma symmetry overlap of the 2p
z
atomic orbitals which gives rise to a bonding 3o
pz

molecular orbital and an anti-bonding 3o
pz
* orbital. Note: the value of the number preceding the
molecular orbital does not have anything to do with the principle quantum number n.






The situation is of course complicated for the second row hetero-nuclear diatomics and second row
molecules (that might contain hydrogen, e.g. H-F). Here the naming is different. First, despite the
fact that the non-hydrogen containing 1s atomic orbitals do not overlap or take part in any bonding,
we still have to acknowledge them to account for the numbering system. We count one of the 1s
atomic orbitals in the second row diatomics as being 1o and the next belongiong to the other atom
as 2o. This then correctly predicts that the next molecular orbital (formed from the constructive
bonding overlap of either two 2s atomic orbitals or by the overlap of a single 2s atomic orbital with
a single 2p
z
atomic orbital) is then labelled the 3o. The antibonding orbital that is also formed (by
the destructive antibonding overlap) is NOT a 3o* and you must work through the molecular orbital
diagram to obtain the correct numbering. The following examples of carbon monoxide and
hydrogen fluoride will make the system clearer. Note also that for heteronuclear diatomics we do
not use the s or p subscripts at all.

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4.5 Molecular orbital energy diagrams for heteronuclear diatomic molecules

Similar energy diagrams can be drawn for heteronuclear diatomic molecules. Two examples will
illustrate the situation.

Carbon monoxide (CO)
Carbon monoxide is isoelectronic to N
2
(i.e. it has the same number of electrons) and it has a
similar energy level diagram to N
2
. However, the atoms have different relative energies for their
atomic orbitals. The resulting mixing between orbitals of the same symmetry means that it is no
longer meaningful to describe the molecular orbitals using the subscript s and p we used in our
earlier diagrams. The dotted lines in the diagram show the principal atomic orbitals from which the
molecular orbital is derived. CO is correctly predicted to have a bond order of 3, and to have no
unpaired electrons.


































E
n
e
r
g
y
A.Os A.Os M.Os
Carbon Oxygen Carbon monoxide
2s
2p
2s
2p

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Hydrogen Fluoride (HF)

In HF, there is a very large difference in the energies of the contributing atomic orbitals.

This means that the characteristics of the resulting molecular orbitals are often very close to the
contributing atomic orbitals. Indeed, the molecular orbitals are derived exclusively from F, and are
termed non-bonding orbitals. There is no overlap of the hydrogen 1s atomic orbital and the
fluorine 2s atomic orbital due to the large difference in energy. Note that the occupied molecular
orbitals in HF are wavefunctions that are principally F in character (i.e. they have a high coefficient
for the F atomic orbitals in the linear combination expression). This accounts for the polarity of the
HF bond; this explanation of polarity doesnt require the nebulous property called electronegativity.
1s
2p
2s
1s
2p
Energy
2s

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4.6 Hybridisation of atomic orbitals

Hybridisation is actually a valence bond concept, but it is sometimes useful in MO theory as well.
Hybridisation may be conceived as the mixing of atomic orbitals on the same atom before
considering orbital overlap with other atoms. [While it turns out to be a useful concept, it does not
actually imply that this mixing occurs in real life!]

Consider methane, CH
4
. The ground state C atom (1s
2
2s
2
2p
2
) 2 unpaired e
-
s for a covalent bond in
valence bond theory. It turns out that it is not too energetically unfavourable to promote one of the
2s electrons into the vacant 2p orbital. The four unpaired electrons can then be shared with the four
hydrogen atoms to form four equivalent covalent












It is thus convenient to describe the configuration of carbon as being derived from four equivalent
sp
3
hybrid orbitals. The energy of a hybrid orbital is the weighted average of the contributing atomic
orbitals. It turns out that the shapes of sp
3
hybrid orbitals point towards the corners of a tetrahedron.
The molecular orbitals of methane may thus be considered to arise from the overlap of the hydrogen
1s orbitals with the carbon sp
3
hybrid orbitals:








Similarly hybrid sp
2
orbitals can be invoked to explain the bonding and the planar geometry of
ethene, C
2
H
4
, with the electrons in the remaining 2p orbital on each carbon atom overlapping
sideways on to form a bond
1s
four equivalent sp
3
hyb. C
1s
four equivalent sp
3
1s
four equivalent sp
3
hyb. C
three equivalent 2p
1s 2s
g.s. C
three equivalent 2p
1s 2s
three equivalent 2p
1s 2s
g.s. C
1s
three equivalent sp
2
2p
1s
three equivalent sp
2
2p

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For ethyne, C
2
H
2
, on the other hand, sp hybrid orbitals can be used to account for the linear
geometry and two bonds formed.












More complicated hybridisation schemes are needed for the coordination geometries of other
elements. For instance, the six equivalent orbitals needed for an octahedral coordination (e.g. SF
6
)
can be treated as sp
3
d
2
hybrids.
1s
two equivalent sp two 2p
1s
two equivalent sp two 2p

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4.7 Three-centre two-electron bonds

Earlier on, we mentioned that valence-bond theory couldnt easily explain the existence of species
such as diborane, B
2
H
6
, in which two of the hydrogen atoms are bridging species. Diborane has
a total 12 valence electrons (B: 1s
2
2s
2
2p
1
; H = 1s
1
) and has an approximate tetrahedral
arrangement of hydrogen atoms around each boron atom








For a BH
terminal
group (BH
t
) the bonding can be considered as two (out of four) normal sp
3

hybridised covalent bonds giving a total count of EIGHT of the available twelve electrons in the
whole molecule. In order to understand the bonding of the bridging species BHB, in diborane
we need to consider that the BHB linkage as being formed from the overlap of 3 orbitals.

To obtain the MO diagram for a B-H-B fragment take linear combinations of two Boron sp
3

hybrid atomic orbitals with a single hydrogen atomic orbital, i.e.



















Boron A.O. Hydrogen A.O.


The net result is the 3-center-2-electron bridge bond


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4.8 Limitations of molecular orbital theory

Molecular orbital theory has two main disadvantages.

Energy level diagrams are extremely difficult to construct for larger molecules, and they also cant
easily explain the shapes of any other than the simplest molecules.

- We can get closer and closer to the true wavefunction of a molecule by adding refinements
either to the valence bond approach or to the molecular orbital approach and so, in the limit,
both descriptions are equivalent. The following table gives an indication of the strengths of the
two main bonding theories.

.
-explains 3-centre 2-electron
bonds such as bridging hydrides
-explains metallic bonding well (see
later)
Cannot fully explain bonding in
certain species
Difficult to get geometric
information
Gives information on molecular
geometry (VSEPR)
Gives electronic structure and
information on:
-magnetic properties
-photoionisation
-electron attachement
Gives information on:
-bond strengths
-bond lengths
-force constants
A bond results from electrons
occupying molecular orbitals
formed from the favourable
overlap of atomic orbitals of
appropriate symmetry
A bond is a shared pair of
electrons
Delocalised description Localised description
MO theory VB theory
-explains 3-centre 2-electron
bonds such as bridging hydrides
-explains metallic bonding well (see
later)
Cannot fully explain bonding in
certain species
Difficult to get geometric
information
Gives information on molecular
geometry (VSEPR)
Gives electronic structure and
information on:
-magnetic properties
-photoionisation
-electron attachement
Gives information on:
-bond strengths
-bond lengths
-force constants
A bond results from electrons
occupying molecular orbitals
formed from the favourable
overlap of atomic orbitals of
appropriate symmetry
A bond is a shared pair of
electrons
Delocalised description Localised description
MO theory VB theory

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5 Bonding in Solids

5.1 Types of solid

Both valence bond and molecular orbital theory are useful descriptions of bonding in solids. Solids
may be classified as:

- Ionic solids
here an infinite structure is formed by bonds that have substantial ionic character (e.g. NaCl). The
coordination number around each atom can often be predicted by the radius ratio rule based on the
ionic radii of the species involved:
o r
smaller
/r
larger
> 0.7 coordination number = 8 e.g. CsCl
o r
smaller
/r
larger
= 0.4-0.7 coordination number = 6 e.g. NaCl
o r
smaller
/r
larger
= 0.2-0.4 coordination number = 4 e.g. CuCl
(note that r
smaller
is almost always that of the cation and r
larger
that of the anion).

- Covalent macromolecules
here an infinite structure is formed by bonds that are essentially covalent (e.g. diamond, SiO
2
).

- Metals
metallic bonding is treated in more detail below, and is best explained by molecular orbital theory.
Virtually all metals exist in one of the three following forms:
o body-centred cubic (bcc): coordination number = 8
o face-centred cubic (fcc; sometimes called cubic close-packed, ccp): coordination
number = 12 (ABCABC packing)
o hexagonal close-packed (hcp): coordination number = 12 (ABAB packing)





















HCP (e.g. Co,Zn)
FCC
(Ag, Ca)
BCC
(Ba, Cs)
HCP (e.g. Co,Zn)
FCC
(Ag, Ca)
BCC
(Ba, Cs)

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- Molecular solids

these are solids in which there are only weak interactions between the molecules (the bonds within
the molecules themselves will be strong). These solids will normally have low melting points (some
of them will exist only at low temperature). The weak interactions may be due to:

o Hydrogen bonds a hydrogen bond consists of an H atom between atoms of more
electronegative non-metallic elements (e.g. OH

O in ice). Note bridging hydrides

in boranes BHB and metallic complexes MHM are not treated as hydrogen
bonds.

o Polar interactions here the molecules have a permanent dipole moment, and so
there will be Coulombic interactions between them
+
AB

+
AB

o Van der Waals interactions here the molecules dont have a permanent dipole
moment, but they can possess a temporary dipole moment which gives rise to a weak
attractive interaction. (e.g. P
4
, S
8
, C
60
)











Solids may be:


- crystalline
here there is long-range order and a regular unit cell is periodically throughout the structure. Ionic
solids and metals are always crystalline. The other solids may or may not be crystalline.


- Amorphous
here there is no long-range order and thus no periodic repeating unit.


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5.2 Molecular orbital theory for solids
Molecular orbital theory can obviously be applied to solids, and it turns out to be particularly useful
in describing the properties of metals. In molecular orbital terms, we treat solids as being very large
molecules (typically containing ~10
23
atoms). We need to consider overlap of the valence atomic
orbitals on each atom in order to generate the molecular orbitals. Thus it is possible for a valence
electron to be delocalised throughout the entire solid. (We can assume that overlap of the inner core
atomic orbitals is negligible).

Consider the molecular orbitals formed from the overlap of a linear chain for 2-11 Li 2s atomic
orbitals between 2 and 11.

















-width of band represents strength of interaction/overlap between A.O.s






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-closer atoms become, stronger is interaction resulting in lowering, in energy of most bonding C.O.s
-and raising in energy of most anti -bonding C.O.s.

















When the number n gets very large (as in a solid), we refer to the resulting molecular orbitals as
forming a band. The band will have finite energy width, but it consists of a very large number of
bonding and antibonding M.O.s that approximate a continuous distribution. The M.O.s that form
the band throughout a whole sample are also know as CRYSTAL ORBITALS (C.O.s). A more
detailed analysis shows a clustering of bonding M.O.s and antibonding M.O.s at the extrema of the
band, leading to the so called density of states. Hence for Lithium the band is half filled BUT not
evenlythe majority of electrons cluster in C.O.s at the lower energy end.






















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5.3 Electrical Conductivity
5.3.1 Metals
Simply put, this occurs when electrons can move through bands following the application of a
voltage (or potential difference)! Consider the following diagram as snapshots of conduction:












































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Overlap of other orbitals

We have seen that the overlap of Li 2s atomic orbitals produces a band whose C.O.s are half full of
electrons and how indeed this facilitates the conduction of electrons. What about Beryllium?
Beryllium has 2 valence electrons in its outer 2s shell and would thus produce a band that would be
completely filled and thus not allow conduction! However, we know that Beryllium is an excellent
conductor, so how can this be? Well, we need to consider so-called Band Overlap. For Beryllium:

































The above diagram shows that the strength of the bonding can be increased if electrons from the top
(anti-bonding) C.O.s are transferred to the bottom (bonding) C.O.s of the p-band. Hence this
accounts for partially filled bands which intern gives Beryllium is electrical conductivity when a
voltage is applied.




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5.3.2 Insulators
For an insulator the valence band (i.e. the band occupied by the valence electrons) is completely
filled, and there is a large energy gap before the next band can be occupied. In this case, electrons
will be unable to move throughout the structure, as the Pauli exclusion principle stops the electron
changing molecular orbital.

For instance, in NaCl, if we take the number of chlorine atoms to be n. The n Cl

ions are very

close to each other. We have 7n valence electrons from chlorine, and 1n valence electrons from
sodium. This means that a continuous band/Crystal orbital will be formed by overlap of the 3s and
the three 3p atomic orbitals based on the chlorine atoms. This will create 4n energy levels where n is
the approximately Avagadros number. These will be sufficient to fill completely the 4n energy
levels created by overlap of the chlorine atomic orbitals. There will also be a band due to sodium
atomic orbital overlap. However, this is far higher in energy (on the basis of ionisation energy,
electron affinity, and/or electronegativity).


































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5.3.3 Intrinsic semiconductors

An intrinsic semiconductor would have a filled valence band at a temperature of absolute zero.
However, the band gap to the next available energy band is not very large, and thermal energy is
sufficient to promote some electrons up into it.

























This means that at high temperatures, a small number of electrons will be able to move easily into
other molecular orbitals (this applies in both the conduction band and at the top of the valence
band), and so conductivity will be observed when a voltage is applied. Unlike metals the
conductivity of semiconductors increases with increasing temperature.













Small band gap (~1 eV)
Valence band

Conduction band

at T = 0
at T > 0

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5.3.4 Doped semiconductors

It is possible to add deliberately a very small amount of a dopant into an otherwise pure material.
For instance a small amount of arsenic can be substituted onto the silicon sites of pure silicon. In
this case each arsenic atom provides an extra valence electron that has to be accommodated. At
absolute zero, these extra electrons will be located on the arsenic atoms themselves (the arsenic
band will be very narrow, as As-As interactions will be negligible, i.e. they behave almost as As
atoms). However, at higher temperatures, the extra electrons may easily be promoted into the silicon
conduction band.

Even a doping level as low as 1 atom in 10
9
can cause
substantial changes in conductivity.






















Doping arsenic into silicon produces what is termed an n-type semiconductor (in which the
principle charge carriers are electrons).










Valence band (Si)

Conduction band (Si)

Donor band (As)

at T = 0
at T > 0

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Doping gallium into silicon on the other hand would produce a p-type semiconductor. As gallium
has a lower valency than silicon, this creates a narrow acceptor band which has an energy just above
the valence band. Thermal excitation of electrons into the gallium band will thus enable electron
transport, effectively by having introduced positively charged holes into the silicon valence band.







Valence band (Si)

Conduction band (Si)

Acceptor band (Ga)

at T = 0
at T > 0

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DIAMONDS!!


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74
6 Transition metal chemistry (a.k.a d-block chemistry)

Transition metals and their compounds are extremely important in nature. The key aspect to the
chemistry of transition metals is the properties of the d orbitals. d electrons are relatively easily lost
and gained, and so transition metals may show a wide range of different oxidation states in their
complexes. Such redox behaviour is often very important in catalysis. [Note: reduction = gain of
electrons; oxidation = loss of electrons]. The presence of the d electrons also normally accounts for
the colour of transition-metal complexes.


6.1 Oxidation Number
The oxidation number is often defined as the apparent ionic charge a particular atom would have if
the compound was ionic. An alternative (and normally equivalent definition) is that it is the charge
remaining on the central metal atom if all the surrounding groups are removed in their closed shell
configuration. There are a range of metal halides, oxides and oxyanions in which the transition
metal has a high oxidation number. These include OsF
6
, CrO
3
, [VO
4
]
3
and [MnO
4
]

. In these cases,
the bonds around the metal are normal covalent bonds.

OXIDATION NUMBER = {Complex Ion Charge (ligand charge) }




















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There are also a wide range of coordination complexes that involve the transition metal in a low
oxidation number. In these cases, the metal is acting as an acceptor of a pair of electrons (i.e. as a
Lewis acid) and the binding group is acting as a donor of electron pairs to form a dative bond. The
binding groups in these cases are commonly referred to as ligands.

Common ligands
neutral
C: CO C
2
H
4
dienes/trienes
N: NH
3
NR
3
pyridine
P: PH
3
PR
3

O: OH
2
OR
2

S: SH
2

Anionic:
H: H

C: CN

CH
3

Ph

Si: SiR
3

N: NH
2

NCS

O: OH

OR

OCOR

ONO

OClO
3

S: SH

SR

SCN

Hal: F

Cl

Br

Cationic:
N: NO
+


Some ligands are bidentate, which implies that they have two donor atoms that can bind to a metal
simultaneously. For example 1,2-diaminoethane (old name ethylene diamine, commonly
abbreviated en) may bind to the metal through both of its amine groups:


















When a ligand binds through two or more donor atoms, the ligand is referred to as a chelate.
Examples of ligands that are tridentate and higher are also known.


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6.2 Electron configuration

Counting the number of electrons around a transition metal is less easy than main group elements.
In general:

- Take the number of valence electrons for a neutral atom (from periodic table). Subtract the
oxidation number. Then add the number of electron pairs in bonds around the metal.

- Example: [Co(III)Cl
2
(NH
3
)
4
]
+







Transition metals do have a preference for adopting the electronic configuration of the nearest noble
gas in the same way as we discussed earlier, and this is sometimes termed the eighteen-electron rule.
For instance, the rule explains the stoichiometries of many transition-metal carbonyl complexes:


Cr(CO)
6





Fe(CO)
5





Ni(CO)
4





However, there are quite a large number of exceptions. For instance:

- steric factors may prevent an 18-electron species being formed.

- electronic factors (that are well understood, but too complicated to go into here) mean that some
complexes are stable 16-electron species (e.g. d
8
species such as Ni/Pd/Pt in the +2 oxidation
state).




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6.3 Shape

VSEPR theory is not appropriate for transition-metal complexes as any d-orbital electrons not
involved in bonding do not form spatially defined lone pairs. The best guess of molecular
geometry is simply to place all the ligands as far apart as possible, with bulkier groups taking
up more space. Thus the geometry around the metal centre of [Cr(H
2
O)
6
]
3+
is octahedral.

















For transition-metal complexes there is a far greater likelihood of electronic factors affecting the
shape. For instance, there is an electronic driving force for 4-coordinate complexes of d
8
metals
(sometimes for Ni, and almost always for Pd and Pt) to adopt a square planar conformation, even
though this is sterically less favoured than the tetrahedral arrangement.





















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6.4 Metal-metal bonds

Some species have direct bonding between metal atoms. As well as overlap between s and p
orbitals, we now also have the possibility of overlap between d orbitals of the correct symmetry to
form energetically favourable bonds.

Co
2
(CO)
8
contains a bond between the cobalt atoms and bridging CO species:

































Note that Co(CO)
4
would have 17 electrons and thus be unstable. Hence this is why Co(CO)
4

dimerises so that each Cobalt atom has a share of eighteen electrons.




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[Re
2
Cl
8
]
2
contains one , two and one bond between the rhenium atoms














Re
Re
Re Re
Re
Re
Re Re
Re Re
z
z
z
z
x
y
x
y
x
y
x
y
+
+
-
-
+
+
-
-
+
+
-
-
+
+
-
-
+
+
-
-
+
+
-
-
-
-
+
+
-
-
+
+
+
+
-
-
+
+
-
-
-
-
+
+
-
-
+
+
+
+
+
+
+
+
+
+

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80

6.5 Cluster compounds

The existence of metal-metal bonding and bridging species leads to a whole variety of complexes
with clusters of metal atoms. Some of these are potential catalysts, while others can be considered
models of what happens at bulk metal surfaces
- Example: Co
3
(CH)(CO)
9
(using M to denote cobalt atoms)


M M
O

C
OC
O

C
C

O
CO
C

O M
C
H
C

O
C

O
C

O

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81
6.6 Metal- ligand bonding (binding)
carbon monoxide
The binding of CO to transition metals is of particular importance both biologically (e.g. to
haemoglobin) and in catalysis (e.g. to the Cu/ZnO surface in the transformation of H
2
+ CO to
methanol). There are two contributions to the bonding:
































- There is a 5
*
-donor interaction from the carbon electron pair into an empty metal orbital. (Note
that the HOMO of CO has electron pair density on the carbon atom, see p. 56).
- There is a back-bonding from electrons in a filled d-orbital on the metal to the empty 2*
LUMO orbital on the CO.
- Thus CO acts as a donor and a acceptor, with these two effects reinforcing each other.
- Evidence: X-ray crystallography shows a shortening of the MC bond and a lengthening of the
CO bond compared to that expected, while spectroscopy shows that the CO bond is weakened.
- Similar considerations apply to the binding of CN

and N
2
to transition metals (as these are
isoelectronic with CO).


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82
Ethene

Another important example of back-bonding is the bonding of alkenes to transition metals. These
may be typified by Zeises salt, [K] [PtCl
3
(H
2
C=CH
2
)].H
2
O, which was first prepared in 1827, but
the structure of which wasnt established until the 1950s.




































- There is donation from the electrons in the C=C bond to the metal centre.
- There is back-bonding from a filled metal d orbital into the * orbital of the alkene.
- Evidence: increase in length of C=C bond.



Pt
C
C
z
x
y
++
Pt
C
C
z
x
y
+
-
+
-

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83

6.7 Organometallic compounds

The last example has moved us into the realm of organometallic chemistry, which is the study of
compounds that contain at least one MC bond (though carbonyl complexes are sometimes
excluded).

One interesting class of molecules are sandwich complexes such as Cr(C
6
H
6
)
2
.






























- Donation of electrons from filled molecular orbitals on benzene into empty d orbitals on
chromium
- Back-donation of electrons from filled d orbitals on chromium into empty * molecular orbitals
on benzene.
- As a result, the reactivity of the benzene ring in this complex will be different in this complex to
that of pure benzene.

A negatively charged cyclopentadienyl ring has aromatic properties like benzene and can bind to
transition metals in a similar way. For instance, the sandwich molecule ferrocene, Fe(C
5
H
5
)
2
, is

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84
particularly stable (it survives up to 500C). Its discovery in 1951 caused the start of research in this
particular branch of chemistry.















It needs to be emphasised that organometallic compounds should not be viewed as outlandish or
unusual. Many are stable species, and some of them have commercial applications in the real
world. For instance the half-sandwich complex (C
5
H
4
CH
3
)Mn(CO)
3
has been widely used as an
anti-knock additive in gasoline in North America. Metallocene complexes such as Ti(C
5
H
5
)
2
Cl
2
are
widely used as catalysts in the preparation of polymers such as polyethylene.