How to describe the behavior of an

electron?
Replace well-defined trajectory of a particle
by a wave function. This tells us how
probable it is that an electron is at a
particular place at a given time.
It is given the symbol (Greek letter psi)
Probability of finding a particle in any
Physical significance of (Max Born)
region of space is proportional to the
square of the wave function (2)
Illustration of the Born (Probability)
interpretation of the wave function:
The square of wave function

Node Wave function

Wave function () can have positive or negative

values. Probability is always positive

When = 0, the probability is also 0-this is

called a
NODE.
Schrdinger Equation
Erwin Schrdinger used the
concept of the wave
function to produce a
mathematical equation to
calculate the behavior of
an electron (or other
particle).
We are not going to worry
about the nature of this
equation (this will be done
later in the course). Just
about the answers that can
be obtained
Summaries of key points from the
Schrdinger equation

The allowed wave functions are found

by solving the Schrdinger wave
equation for the particle.
Solution of the Schrdinger wave
equation is only possible for certain
energies.
The probability density for a particle at
any point is proportional to the square
of the wave function at that point.
Atomic Spectra

Introduction to spectroscopy later in Semester

Basic principle:Excited state 2
Excited state 1
Energy
h1 h2
Ground state
Going from higher to lower energy state-
emission of photon (h) corresponding to
energy gap between levels.
 Long before quantum theory observed that
emission spectrum of H (and other) atoms
consisted of separate lines, i.e. lines
corresponding to discrete energies.

Measurements showed that the lines in the

hydrogen spectrum all fitted the expression:
1 1
R( 2 2 )
n1 n2
Where n1=1,2,; n2 = n1+ 1 , n1+ 2,
R= Rydgberg constant, 3.29 x 10 15 Hz

This suggests that the energy levels of H

are proportional to R/n2.
Schrdinger Equation for the Hydrogen Atom
Can we explain the hydrogen atomic spectrum using
the Schrdinger equation?

Yes!! we dont need the math's here, but lets look at

the results.
Schrdinger found that only certain wave functions
were allowed

Hydrogen (or other) atom -3 dimensions each allowed

solution was defined by 3 quantum numbers
We are most familiar with Cartesian
coordinates (x,y,z) to describe a position in
space.

In solving the Schrdinger wave equation

for the hydrogen atom it is much more
convenient to use polar coordinates to
define the position of the electron:
Spherical Polar
Coordinates (like latitude
& Longitude)
Each allowed solution (wave
function) of the Schrdinger
equation for the hydrogen atom
defines an allowed
ATOMIC ORBITAL
 Using spherical polar coordinates, every
allowed wave function for the hydrogen atom
has the same general form:

Rn ,l (r )Yl ,ml ( , )
i.e. the whole function is separable into TWO
parts:
RADIAL WAVEFUNCTION R
Depends only on r (distance from nucleus)

ANGULAR WAVEFUNCTION Y
Depends only on orientation with respect to axes
(,) and determines the shape.
Before we explain the significance of the
RADIAL and ANGULAR WAVEFUCTIONS
it is necessary to explain the subscripts
in the above equation for .

They are in fact the Quantum

Numbers for the
Hydrogen Atom

Remember, solutions to 3-dimensional

Schrdinger equation three quantum
numbers.
Labeled as

n, l, ml,
Each set of specific values for these
quantum numbers defines the
ORBITAL occupied by an electron

What are the allowed values for,

and the physical significance of,
each of these quantum numbers?
n is the PRINCIPAL QUANTUM NUBER

Allowed vales: 1,2,3,4,5,.(0 is NOT

allowed).

For hydrogen atoms (and other species with just 1

electron, i.e He+ , Li2+ etc.), n ALONE determines the
ENERGY of an allowed solution of the wave equation
The expression for the energy is
2
E cz 2 kJmol 1
n
Where E= energy,
z= nuclear charge (1 for H,2 for He+ etc.)
n= PRINCIPAL QUANTUM NUMBER
c= Constant

n also determines the overall SIZE of the orbital

- See later.
 Energy defined as zero for free electron.

All energies for bond electrons is NEGATIVE.

Energy to remove electron from

Energy levels for the
atom (n= 1 ) is called the
IONISATION ENERGY.
Hydrogen Atom
These calculated energy levels agree agreed exactly with
those
ured measured experimentally in the atomic
spectrum of H
 l is the SUBSIDIARY or ORBITAL ANGULAR
MOMENTUM QUANTUM NUMBER
Allowed values: 0, 1, 2, (n-1)
i.e for n = 1 l = 0 only
20 or 1
30, 1 or 2
40, 1, 2, or 3
etc.
l determines the SHAPE of the orbital (see
later),
But for one-electron atoms has NO effect
on the energy
Orbitals labeled according to l value:
l 0 s orbital
1 p orbital
2 d orbital
3 f orbital
4 g orbital)
(and then alphabetical)
Hence, the following orbitals are
possible.
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f

i.e. no 1p, 2d, etc. --- because

maximum value of l is (n-1).
NOTE:
ENERGIES OF HYDROGEN- LIKE
ATOMS:

1s < 2s = 2p < 3s = 3p = 3d
< 4s = 4p = 4f <

Orbitals of the same energy are

described as DEGENERATE
m, is the MAGNETIF QUANTUM
NUMBER
When the subsidiary quantum number has a value
of l the allowed values of m, are:

-l, -l+1, -l+2, -1, 0, 1, 2, .. +l-1, +l

i.e. (2l+1) values for a given value of l.

m, determines ORIENTAITON in space of an

orbital
m has NO effect on energy of electron (except in
a magnetic field hence the name).

Numbers of orbitals:(2L+1)
s (l = 0) 1 (m = 0)
p (l=1) 3 (m = -1,0,+1)
d (l=2) 5 (m = -2,-1,0,+1,+2)
f (l=3) 7 (m = -3, -2,-1,0,+1,+2,+3)
i.e. there will be three 2p orbitals (all degenerate),
five 3d orbitals (also degenerate), seven 4f
orbitals (also degenerate) etc.
What do we mean by SIZE, SHAPE and
ORIENTATION of orbitals?

We must go back to the radial and angular

wave functions

RADIAL WAVEFUNCTIONS

See mathematical forms in your recommended

books
we will just look at the graphs obtained by plotting
R(radial wave function) against r (distance of
electron from nucleus):
The radial parts of the wave functions for n = 1, 2, and 3

We are more interested in the probability of finding the

electron at a given distance r from the nucleus.
Remember probability (wave function)2
and also note that the area of a sphere of radius r
is given by 4r2.
 To show the probability of finding an electron
in a spherical shell at a distance r from the
nucleus, we plot 4r2R2 against r. This gives
us the Key features:

To show the probability of

1. finding an have a
All s orbitals
finite amplitude
RADIAL
electron
at the in PROBABILITY FUNCTIONS
a spherical shell at a distance
nucleus. r
from the nuclleus, we plot 4r2R2 against r.
This gives us the 2. All orbitals decay
exponentially at
sufficiently great
distances from
the nucleus.
Some further points about radial probability functions:
1. As n increases for a given l, the distance of
maximum probability increases, i.e. SIZE INCREASES.

2. There is a small probability, but>0 of finding an

electron a long way from the nucleus, therefore an
accurate definition of size is not easy.

3. There are often distance from the nucleus with ZERO

probability of finding the electron. These are called
NODES (specifically RADIAL NODES in this case).

The number of radial nodes = n - l - 1,

i.e. 0 for 1s, 2p, 3d; 1 for 2s, 3p, 2for 3s.
To consider SHAPE and ORIENTATION of
orbitals, we need to look at the

ANGULAR WAVEFUNCTIONS

Because the radial wave function shows the

possibility of finding electron (occasionally) a
long way from the nucleus
- We have to make an arbitrary definition of size.
A surface is drawn to enclose 90% of the total
electron probability
With this definition we can plot the Y2 (angular
probability functions) values for n=1-3.
Note that the shapes and orientations depend only on
l and m, so that 1s,2s,3s,.. etc. orbitals all have
same shape, as do 2p,3p, , and 3d,4d
 SHAPES OF ORBITALS

These are plots of Y2, but showing the

signs of the wave functions Y.
1s Orbital
2s and 2p Orbitals
Note that there are three different configurations
corresponding to m = -1, 0, 1
Now there are five different configurations
corresponding to m = -2, -1, 0, 1, 2
Notes on angular wave functions /probabilities

1. As shapes are independent of n, all orbitals of

the same type have the same shape, i.e.
1s,2s,3s,. Are all spherical etc.

2. Angular NODES are often present. Number of

angular nodes = l. There fore

TOTAL NUMBER OF NODES (RADIAL +

ANGULAR) = n-1

For the hydrogen atom, exact solutions to the

Schrdinger wave equation give the allowed
energy levels.
For the H atom, the single electron is normally in the
ground state, i.e. in the 1s orbital. If the appropriate
amount of energy is given to the electron, it will be
raised to one of the excited states.

The solutions to the Schrdinger equation explain

completely the atomic spectrum of the hydrogen
atom.

Is it possible to do the same for all other atoms,

i.e. those with >1 electron (MANY-ELECTRON
ATOMS)??
MANY ELECTRON ATOMS
Problem with > 1 electron-cannot solve
Schrodinger equation exactly.

There are ways around this (tell you

about these later in your course)-just
consider results.

Results of calculations on atoms with >

1 electron:
1. As expected, only certain energies
allowed
2. Each allowed solution characterized by
same 3 quantum numbers as H (n, l, ml)
3. Angular wave functions exactly the
same as for H-shapes of s, p, d, f, etc
orbitals same as for H

4. Unlike H, the energies depend on BOTH

n and l. The energies
s < p< (for
d<a f<
given n) are
in the order:

Energies of orbitals for 1-electron atom (H)
1s < 2s = 2p < 3s = 3p = 3d< 4s = 4p
= 4d = 4f<
Energies of orbitals for atoms with >1
electron 4s <
3d
1s < 2s < 2p < 3s < 3p<4s <3d< 4p <
5s < 4d < 5p < 6s < 4f < 5d <

Can we explain the order of energies,

e.g. 3s < 3p < 3d?
Reason for observed order is that
for 3s, and to smaller extent 3p,
the electron spends some time
very close to the nucleus.
Outer electrons are normal SCREENED from
the full effects of the nuclear charge.

However, if an electron PENETRATES inside

the shielding electrons, it is subjected to an
increased EFFECTIVE NUCLEAR CHARGE
Hence, 3s electrons are more tightly bound than 3d.
This is always true, whatever the n value, so we
always have:s < p < d < f<
 The Periodic Table
Great triumph of 19th century Inorganic
chemistry (D.I.Mendeleev, 1869) based on
chemical and physical properties
Can we use the solution to the Schrodinger
Wave equation for hydrogen-like atoms to
explain the periodic Table?
Yes, we can! using the Aufbau Principle

To move from one element to the next,

add one proton and x neutrons to the
nucleus, and one electron into the orbital
of lowest energy which is available
 This brings us to the next question:
How many electrons can we put in any orbital?
To answer this we need to introduce a new
quantum number.

Electrons are found to behave as though they were

spinning. A particle can spin clockwise or
anticlockwise. This spin is defined by Spin
Quantum Number. This has the symbol m s and it
can have only TWO values: + or - .

Thus each electron is completely specified by the

values of FOUR quantum numbers: n, l, m l, and
ms
How does this affect the possible number of
electrons in an orbital?
The Pauli Exclusion Principle
This is a restriction on the allowed
values of the 4 quantum numbers:
No two electrons in system can
have identical values for all 4
quantum numbers

How can this restrict the numbers of

electrons in an orbital?
 All electrons in any orbital, by definition, have
the same values for n, l, and ml.
By the Pauli Principle, each electron in a
particular orbital must have different values of
the four quantum numbers.
But ms can only have TWO values ()

There is a maximum of TWO electrons in any

orbital, and they must have different
(opposed) spins.

Using the Aufbau and Pauli exclusion principle,

we can now start to build up the periodic table.
The Periodic
Table
Using the order of orbital energies
given earlier, we must start with 1s:
H: 1s1 He: 1s2
Spins must be opposed in He. This is
now a FULL SHELL-this is very stable,
hence He is an inert atom, since it is
very difficult to break up a full shell
Li 1s2 2s1
1s 2s 2p

The 2s electron is not held so tightly

(lower ionization energy). Chemistry
of lithium is dominated by tendency
to lose this electron
(Li+) 2
Be 1s 2s2
1s 2s 2p
 Beryllium has a FULL SUB-SHELL- this
is not so stable as full shell, but Be is
still fairly unreactive
2 2 2p1
B 1s 2s
1s 2s 2p
When we go from boron to carbon, we
have several choices for the last
electron.
The next electron will go into 2p, but will
it be:
or or

(a) (b) (c)

If both electrons are in same orbital, they must

have different spins.
We can rule out (a) at once-greater repulsion
between electrons.
How to choose between (b) and (c)?

We must use:
 The most stable
HUNDs electronic state is the
RULE one with the most
Hence (c) is the most stable state.SPINS
PARALLEL
The electronic ground state for carbon is thus:

C 1s22s22p2
1s 2s 2p
That for nitrogen must be:

N 1s22s22p3
1s 2s 2p
Then for oxygen etc.:

O 1s22s22p4
1s 2s 2p
F 1s22s22p5
1s 2s 2p
Ne 1s22s22p6
1s 2s 2p
Neon, like Helium, has a full shell and is
therefore very inert
The chemistry of F is dominated by its
tendency to acquire the electron needed to
obtain a full shell ( F-)
Note the distinction between CORE (inner-shell
electrons, i.e. 1s2 in the series Li-Ne) and
VALENCE ELECTRONS (partly-filled shell electrons
in the highest energy orbital). Only the latter are
affected by chemical changes.
(This is shown dramatically by comparing the
ionization energies of (IE) for H (1s1) and Li
(1s22s1)
H1s1 1s0 requires 1312 kJ mol-1 (1st IE)
Li 2s1 2s0 requires 513 kJ mol-1 (1st IE)
Li+ 1s2 1s1 requires 7298 kJ mol-1 (2st IE)
Both values for first IE are energies attainable in chemical
systems. The second IE is NOT!
 The rest of the periodic table is constructed in
the same way-using the Aufbau principle,
Pauli principle, Hunds Rule, and the order of
orbital energies.

The periodicity of chemical properties arises

because elements with the same number and
type of valence electrons behave similarly.

Thus Na (1s22s22p63s1) is very

similar to lithium (1s22s1)
Chemical
Bonds
A chemical bond is formed between two atoms
if the resulting arrangement of the atoms and
their electrons has a lower energy than the
separate atoms themselves.
Two ways of creating a chemical
bond:

Complete electron transfer IONIC BOND

Electron sharing COVALENT BOND
 IONIC
BONDS:
formed between atoms with low ionization energies
and those with high ELECTRON AFFINITIES, e.g.
Na+Cl-.

You will hear a lot more about ionic compounds

and their properties in later chapter.
We are going to concentrate on

Covalent
Bonding
Characteristic of elements in the middle of the
Periodic Table-complete electron transfer is not
practicable.
Nature of covalent bonding first established
by G.N.Lewis, in 1916, before modern
quantum theory had been thought of.
Lewis idea was that the formation of
covalent bond occurred when one electron
from each atom became shared to form an
ELECTRON PAIR.
For hydrogen we electron
would have:

The two atoms are held together by

the attraction between the pair of
electrons and both nuclei
nuclei
Unequal sharing-polar covalent
bond
Homonuclear bonds when the two atoms
forming a covalent bond are the same-
the electrons will be equally shared.
Heteronuclear bond if the atoms are
different-the sharing will be unequal!
Which atom gets more of the electrons?

Depends on the electronegativities of the

atoms
 Electronegativity Basic definition:
The ability of an atom in a molecule to attract
electron density to itself

How to make this idea

quantitative?
Simplest (Mulliken)
1
( I Ea )
2
Where = electronegativity
I = Ionization energy
Ea = electron affinity