CHEM 101

Fall 2019

Office Hours
Monday From 11:00 to 1:00pm
Friday from 2:00 to 4:00pm
Tutorial
Wednesday from 12:30 to 1:30 pm
Saturday from 6:00 pm to 7:30 pm

Muhammad Azhan
BS Chemistry Batch 2021
Department of Chemistry
SBA School of Science & Engineering
LUMS
CHEM 101
Quantum numbers, orbitals and energies
When we solve the Schrodinger equation we often find that the wave functions and
energy levels are characterized by a particular set of numbers, called
quantum numbers.
By 'characterised' it is meant that if we know the quantum numbers we can fairly
easily work out the mathematical form of the wavefunction and the associated
energy.
Quantum numbers are usually restricted to be integers (0, 1,2 .. . ), or half integers
1/2, 3/2, ....
For the hydrogen atom, it turns out that there are three quantum numbers which
characterize the orbitals:
1. The principal quantum number, n, which takes values 1,2, 3 . . .
2. The orbital angular momentum quantum number, l, which takes
values from (n - 1) down to 0, in integer steps.
3. The magnetic quantum number, ml, which takes values from +l to
−l in integer steps; there are thus (2l + 1) different values of ml (i.e. l
positive values, I negative values, plus a value of zero ).

Chapter 2: Keeler
CHEM 101
Quantum numbers, orbitals and energies
➢ Each separate orbital has a unique set of values of the three quantum numbers n,
l and ml.

➢ A knowledge of these quantum numbers enables us to specify the energy and

three-dimensional shape of the orbital.

➢ It turns out that the energy of an orbital depends only on the value of the
principal quantum number n for one electronic system, so it is common to
group orbitals with the same value of n together into shells.

➢ Traditionally, orbitals with n = 1 are called the K shell, those with n = 2 the L
shell, and those with n = 3 the M shell.

Chapter 2: Keeler
CHEM 101
Quantum numbers, orbitals and energies
The K shell (n = 1)
➢ The orbital angular momentum quantum number l takes values from (n − 1)
down to 0 in integer steps.
➢ Thus, if n = 1 the only value for l is zero. The magnetic quantum number ml
takes values between +l and -l in integer steps, so as l = 0 there is again only
one value, which is ml = 0.
➢ So, in the K shell there is just one orbital with n = 1, l = 0 and ml = 0.
Traditionally this orbital is denoted 1s. The number gives the value of n and the
letter gives the value of l according to Table. This orbital is spherically
symmetric.

Chapter 2: Keeler
CHEM 101
Quantum numbers, orbitals and energies
The L shell (n = 2)
➢ This shell has n = 2, so the maximum value of l is (n − l) which is (2 −1) = 1.
Remember that l can take integer values from this maximum down to zero, so
that l = 0 is also possible.
➢ As we had before, for l = 0 there is only one value of ml, which is zero. This
orbital is denoted 2s, the '2' being the value of n, and the s indicating that l = 0.
➢ For l = 1, there are more values of ml. Recall that the rule is that ml can take
values between +l and -l in integer steps, so there are three ml values: + 1,0 and
−1. These three orbitals are all denoted 2p: the '2' giving the value for n, and the
'p' being the letter for 1 = 1, according to Table. The three 2p orbitals have
different shapes, and they are often denoted 2px, 2py and 2pz.
The M shell (n = 3)
➢ For this shell n = 3, so l can take the values 2, 1 and 0. When l = 2, ml can take
the values +2, +1, 0, −1 and −2: these correspond to the five 3d orbitals, d being
the letter used to represent l = 2.
➢ For 1 = 1 we have as before three orbitals, denoted 3p, and in addition for l = 0
there is one orbital denoted 3s. In total there are nine orbitals in the M shell.
Chapter 2: Keeler
CHEM 101
Radial and Angular Nodes
➢ The s orbitals have no nodal planes or angular nodes, but the number of radial
nodes increases as the principal quantum number increases.
➢ Similarly, as we go from s to p to d orbitals, the number of nodal planes
(angular nodes) increases steadily.
➢ The number of these radial and angular nodes is important as their presence
determines the overall shape of an orbital.
➢ The numbers of the radial and angular nodes, obey the following simple set of
rules.
➢ For an orbital with quantum numbers n and l:
❖ The total number of angular and radial nodes is (n - 1).
❖ The number of angular nodes (nodal planes) is l.
❖ The number of radial nodes is (n - 1 - l).

For example, for a 3p orbital, there are a total of (3 - 1) = 2 nodes. As l = 1 there is

one angular node, and (3 - 1 - 1) = 1 radial node.

Chapter 2: Keeler
CHEM 101
Orbital Energies
➢ The energy of an atomic orbital (AO) in hydrogen depends only on the
principal quantum number n 2
Z RH
En = −
n2
In this expression En is the energy of the orbital with principal quantum number n,
Z is the nuclear charge (here = 1), and RH is the Rydberg constant, which takes the
value 2.180 x 10−18 J, or 1312 kJ mol−l in molar units.

The SI unit for energy is the joule (symbol J), but it is not always convenient to use
this unit, especially when we are dealing with atoms and molecules. The energy of
the electron in the 1s orbital in hydrogen is, from above Eq., − 2.180 x 10−18 J: an
inconveniently small and rather unmemorable number.

If we consider a mole of hydrogen atoms, then the energy is obtained simply by

multiplying the energy of one atom by Avogadro's constant, NA. SO the energy of
the 1s electron is NA x −2.180 x 10−18, which is −1312 kJ mol−1. This is a more
memorable number.
Chapter 2: Keeler
CHEM 101
Trends in bonding
➢ To understand the trends in the bonding between the elements we need to look
at how the energies and sizes of atomic orbitals vary across the periodic table.
➢ The variation in orbital energies across the periodic table can be understood in
terms of the increase in nuclear charge, the extent to which different electrons
screen one another from the nucleus, and the shell to which a particular orbital
belongs.
➢ The concept of the effective nuclear charge experienced by an electron is a
useful way of rationalizing trends in the sizes of orbitals, ionization energies
and electron affinities.
➢ Anomalies are observed in the properties of the elements from Period 2 due to
their small sizes, and in the very heaviest elements from Period 6 due to
relativistic effects.
➢ The structures adopted by the elements can be rationalized in terms of the
number of valence electrons available and the size of the orbitals occupied
by these electrons.
 CHEM 101 Orbital energies & the effective nuclear charge

Orbital energies
➢ What is the trend of orbital energies in a period?

➢ What is the trend of orbital energies in a group?

The effective nuclear charge- Zeff

➢ What is the trend of the effective nuclear charge in a period?

➢ What is the trend of the effective nuclear charge in a group?

➢ What is the effective nuclear charge experienced by the valence

electron in Carbon vs silicon?

➢ What is the orbital energy of the valence electron in Carbon vs

silicon?
Chapter 8: Keeler
CHEM 101
Moving across the second period
Why the 2s falls considerably more steeply than 2p.

Z 2 RH
En = −
n2

➢ The 2s electron is more penetrating that the 2p and so feels the influence of the
nuclear charge more than does the 2p.
➢ As a result, the increase in nuclear charge has a greater effect on the 2s than the
2p, and this explains why the 2s falls more steeply as the nuclear charge
increases.
Chapter 2: Keeler Dr. Ghayoor Abbas
CHEM 101
Moving across the second period
As we move across the remainder
of the period, the 2p sub-shell is
steadily filled, becoming
complete at Ne with the
configuration 1s2, 2s2, 2p6.
There is a steady downward
trend in the energies of the 2s Z 2 RH
and 2p AOs, with the 2s falling En = − 2
n
considerably more steeply.
Why?
These trends can be rationalized by noting that for each successive element the
nuclear charge increases by one, and one extra electron is added. The increase in
nuclear charge will result in a decrease in the energy of the orbitals, but the extra
electron results in an increase in electron-electron repulsion which increases the
orbital energies. As we have already noted, electrons in the same shell do not shield
one another particularly well, so the effect of the increase in nuclear charge
dominates, accounting for the general fall in the orbital energies.
Chapter 2: Keeler
CHEM 101
Moving across the third period
On moving from Ne to Na the
additional electron has to go
into the n = 3 shell, and it is
found that the lowest energy
arrangement is when the
electron goes into the 3s.
i.e. 1s2, 2s2, 2p6, 3s1.
The 3s is more penetrating than Z 2 RH
the 3p.
En = − 2
n
The energy of the 3s in Na is −5.00 eV, somewhat higher than for the 2s electron in
Li (-5.34 eV).
For atoms in the same group in the periodic table, the energies of outer electrons
are always higher for the element with higher n value. For example, the energy of
the 3s orbital in Si is higher than the 2s in C, and similarly the 3p is higher than the
2p. This indicates that it is the change in principal quantum number n which
dominates the difference in energy between 2p in C and 3p in Si; any change in the
effective nuclear charge is of secondary importance.
Chapter 2: Keeler
CHEM 101 Z 2 RH
Moving across the fourth period En = −
n2

For the elements potassium

(K) to zinc (Zn) the energy of
the 4s AO only decreases by
a total of about four eV over
the twelve elements.
An explanation for this is
that between scandium (Sc)
and copper (Cu) electrons are
being added to 3d orbitals,
and such electrons form an
effective screen for the 4s
electrons.
In short, as far as the 4s electrons are concerned, on moving
from one element to the next between scandium and copper,
the effect of the extra proton added is largely cancelled out
by the addition of the electron to the lower 3d orbital.
Consequently the energy of the 4s falls rather slowly.

Chapter 8: Keeler
CHEM 101 Z 2 RH
Moving across the fourth period En = −
n2

From gallium (Ga) onwards,

extra electrons are being
added to the 4p orbitals.
These do not screen the
electrons in the 4s orbitals as
efficiently as do electrons in
the 3d.
Hence, from gallium to
krypton (Kr), the energy of
the 4s orbital drops far more
rapidly as the 4s electrons
experience more of the
effect of the additional
proton.
We see from the graph that the energy of the 4s orbital
drops by more than 20 eV over the series of just six
elements.
Chapter 8: Keeler
CHEM 101
Variation within the same group

For atoms in the same group in the periodic table, the energies of outer electrons
are always higher for the element with higher n value. For example, the energy of
the 3s orbital in Si is higher than the 2s in C, and similarly the 3p is higher than the
2p. This indicates that it is the change in principal quantum number n which
dominates the difference in energy between 2p in C and 3p in Si; any change in the
effective nuclear charge is of secondary importance.
Chapter 2: Keeler
CHEM 101 Anomalies in orbital energy trends across groups

➢ Energies of the s and p orbitals for the second period elements

seem to be lower than expected when compared to the energies of
s and p orbitals for the later members of the groups.
➢ There is a downwards kink in the orbital energy on moving from
the 3s (green circles) to the 4s (red circles).
➢ The energy of the 6s orbital for the period six elements is
somewhat lower than the energies of the 5s orbitals from the
previous row.
CHEM 101 Summary: Anomalies in orbital energy

➢ Anomalies are observed in the properties of the elements of the

following periods.
▪ Low s & p orbital energies of ▪ due to small n value
the elements of the Period 2
❖ Low orbital energies of the ❖ due to incorporation of
elements of Period 4 d orbitals
❑ in the very heaviest elements ❑ due to relativistic effects &
from Period 6 incorporation of f orbitals
CHEM 101 Orbital energies - The second period anomaly

An important feature to notice from Figure is that the energies of the s

and p orbitals for the second period elements seem to be lower than
expected when compared to the energies of s and p orbitals for the
later members of the groups.
For example, whilst there is a gradual increase in the sand p orbital
energies for the series S-Se-Te-Po, there is a much sharper increase
between oxygen and sulfur.
CHEM 101 Orbital energies - The second period anomaly

The reason why the sand p orbitals for the

elements in the second period are so low in
energy is usually attributed to the particularly
small value of the principal quantum number (n
= 2).
Since the orbital energy is proportional to -1/n2,
a small value of n (either one or two) means that Z2 RH
En = −
the energy ends up rather large and negative. n2

This effect is illustrated in Figure which shows a plot

of −1/n2 against n. The biggest jump is from when n
= 2 to n = 3, with a more gradual rise from then on.
Even though we have not included any effective
nuclear charges, we see that the graph mimics the
increases in energy seen in previous Figure.
Chapter 8: Keeler
CHEM 101
Degeneracy
➢ The energy of an atomic orbital (AO) in hydrogen depends only on the
principal quantum number n 2
Z RH
En = −
n2
➢ A rather special feature of these orbitals for hydrogen is that the energy depends
only on the value of the principal quantum number.
➢ This means that the 2s and 2p orbitals have the same energy, as do the 3s, 3p
and 3d orbitals.
➢ In quantum mechanics, wavefunctions which are different but have the same
energy are described as being degenerate. So the 3s, 3p and 3d are described as
degenerate orbitals or wavefunctions.
.
➢ We will see later on, though, that in multi-electron atoms this degeneracy is lost.

Chapter 2: Keeler
CHEM 101
Screening
Screening is simply a
consequence of electron-
electron repulsion.
The distant 2s electron
experiences an attraction
due to the nuclear charge of
+3, and a repulsion from
each 1s electron due to their
charge of −1.
If the latter are clustered
close enough to the
nucleus, the repulsion due
to the two electrons cancels
out completely two units of
the positive charge on the
nucleus, leaving an effective
nuclear charge, Zeff, of + 1.

Chapter 2: Keeler
CHEM 101
Screening
If the screening by the two
1s electrons is perfect, then
the 2s electron in Li is
essentially in a one-electron
atom with a nuclear charge
+1; 2
Z RH
En = − 2
n
(12 )(13.6eV )
− 2
= −3.4eV
2
The actual energy of the 2s in Li is −5.34 eV, which is
significantly lower than the energy we have just
computed.
We interpret this result by saying that the screening by
the two 1s electrons is not perfect, so the 2s electron
experiences an effective nuclear charge which is
greater than +1.
Chapter 2: Keeler
CHEM 101
Penetration
If we refer again to the RDFs for the 1s
and 2s in Figure, we see that a small part
of the electron density for the 2s does
indeed fall inside the region occupied by
the 1s.
In other words, there is some
probability that the 2s electron 'gets
inside' the screen formed by the 1s2,
thus experiencing more of the nuclear
charge.

This is usually described by saying that

the 2s electron penetrates to the
nucleus. So the probability of finding
the particle closest to the nucleus is
penetration

Chapter 2: Keeler
CHEM 101 Effective Nuclear Charge, Zeff
One useful approach to quantifying the extent of shielding and penetration is to
rewrite orbital energy equation using not the actual nuclear charge but an effective
nuclear charge, Zeff.
2
Z 2 RH Z eff RH
En = − 2 E n ,l = −
n n2
We then rearrange this so that given the orbital energy, En, we can compute Zeff.
We Know E2s (Li) = -5.34 eV
 n E n ,l 
2

Z eff = − 
R  22 (−5.34eV ) 
 H  Z eff = −  = 1.25
 (13.6eV ) 
Using this equation we find Zeff for 2s in Li to be 1.25.
That this value is greater than 1 indicates that the screening is not perfect i.e. the 2s
has penetrated the 1s2 shell somewhat.
However, Zeff is much less than the actual nuclear charge of +3, indicated that the
Is electrons are pretty effective at screening the nucleus.
Chapter 2: Keeler
CHEM 101
Penetration
Why the ground state configuration of Li is1s2, 2s1 and not 1s2, 2p1?

Recall that in a one-electron atom the 2s and 2p orbitals are

degenerate i.e. have the same energy, but this is no longer
Z 2 RH
the case in Li, where the configuration of the ground state En = −
shows that occupation of the 2s gives a lower energy than n2
occupation of 2p.
Chapter 2: Keeler
CHEM 101 Effect of the Charge on the Nucleus
➢ In fact, the energies and the wavefunctions change in rather a 2
simple way as the charge on the nucleus, Z, increases. As we E n = −
Z RH
saw in the following Equation, the energies go as Z2, where Z n2
is the nuclear charge:
➢ Thus, as the nuclear charge increases,
the energies of the orbitals all
decrease (become more negative).
For example, the 1 s orbital of He+
has an energy of −4RH compared to −
RH for hydrogen.

Fig. 2.39 Plots of the RDFs for a 1s

electron with increasing nuclear
charge, Z. As Z increases the orbital
is pulled in towards the nucleus and
so becomes more compact.

Chapter 2: Keeler
CHEM 101
Slater's rules
Slater's rules are an approximate method for estimating the effective
nuclear charge. Slater proposed that Zeff could be written as,
Zeff = Z − S
where Z is the actual nuclear charge and S is a shielding constant,
which is computed in the following way.
First we divide up the orbitals into groups (indicated by the brackets)
and order them as follows.

(1s) (2s, 2p) (3s, 3p) (3d) (4s,4p) (4d) (4f)…………..

In this grouping, sand p orbitals with the same principal quantum
number are grouped together, but d and f orbitals are separated.
The value of Z is known from atomic number. The value of shielding
constant S needs to be determined to calculate Zeff.
CHEM 101 Slater's rules
Zeff = Z − S (1s) (2s, 2p) (3s, 3p) (3d) (4s,4p) (4d) (4f)…..
The value of S of a particular electron (in a particular group) is
computed using the following rules:
1. There is no contribution to S from electrons in groups to the right
of the one being considered.
2. A contribution of 0.35 is added to S for each electron in the same
group as the one being considered, except in the (1s) group where
the contribution is 0.30.
3. If the electron being considered is in an ns or np orbital, then
electrons in the next lowest shell (i.e. that with (n − 1)) each
contribute 0.85 to S. Those electrons in lower shells (i.e. (n − 2)
and lower) contribute 1.00 to S.
4. If the electron being considered is in an nd or nf orbital, all
electrons below it in energy contribute 1.00 to S.
CHEM 101 Slater's rules
These rules encapsulate the ideas we have been exploring in this
section.

➢ Rule 1 says that electrons in higher orbitals do not contribute to

the screening e.g. 2s electrons do not screen 1 s electrons.
➢ Rule 2 says that electrons in the same shell shield one another to
some extent.
➢ Rule 3 says that electrons in the next lower shell are quite good at
screening the nuclear charge, and those in the shell below that (if
there is one) form a perfect screen e.g. for a 3s electron the 2s
form a good screen, and the 1 s form a perfect screen.
➢ We shall discuss Rule 4 when we consider transition elements in
more detail.
CHEM 101
Slater's rules
These rules encapsulate the ideas we have been exploring in this
section.

➢ Rule 1 says that electrons in higher orbitals do not contribute to

the screening e.g. 2s electrons do not screen 1 s electrons.
➢ Rule 2 says that electrons in the same shell shield one another to
some extent.
➢ Rule 3 says that electrons in the next lower shell are quite good at
screening the nuclear charge, and those in the shell below that (if
there is one) form a perfect screen e.g. for a 3s electron the 2s
form a good screen, and the 1 s form a perfect screen.
➢ We shall discuss Rule 4 when we consider transition elements in
more detail.
CHEM 101
Slater's rules
Q: Calculate the effective nuclear charge experienced by the 1s and
2s/2p electrons in carbon using slater’s rules.
Carbon electronic configuration: (1s2) (2s2, 2p2)
Zeff = Z − S For Carbon Z = 6.
For Zeff (1s), following Slater's rules the 2s and 2p make no
contribution to S (Rule 1), but according to Rule 2 we have a
contribution of 0.30 to account for the effect of the other electron.
Zeff (1s) = 6 − 0.3 = 5.7
To calculate Zeff(2s), Rule 1 does not apply and Rule 2 says that we
have a contribution of 0.35 for the other three electrons in the same
group. Rule 3 says that each 1s electron, as it is in the next lowest
shell, contributes 0.85.
Zeff (2s) = 6 − (3 x 0.35) − (2 x 0.85) = 3.25
CHEM 101
Slater's rules

Zeff = Z − S Carbon electronic configuration: (1s2) (2s2, 2p2)

The effective nuclear charge experienced by the 1s and 2s electrons
in carbon using Slater’s rules. Zeff (1s) = 5.7 Zeff (2s) = 3.25
➢ The values for Zeff obtained from modern calculations are 4.8 for
1s, 2.4 for 2s and 1.9 for 2p.
➢ Slater's rules give values which are in the right ball park, but the
numerical agreement is not good.
➢ In particular, these rules predict Zeff to be the same for 2s and 2p,
which is not the case.
We should not be too critical of Slater's efforts: the interactions
involved in multi-electron atoms are subtle and complex, so we
cannot reasonably expect an accurate prediction of Zeff based on a
simple set of rules.
CHEM 101
Slater's rules
Q: Calculate the effective nuclear charge experienced by the 1s,
2s/2p, and 3s/3p electrons in silicon.
Silicon electronic configuration: (1s2) (2s2, 2p6) (2s2, 2p2)
Zeff = Z − S For Silicon Z = 14.
For Zeff (1s): Zeff (1s) = 14 − 0.3 = 13.7
i.e. the 1s electron feels most of the nuclear charge.
For Zeff (2s/2p):
For a 2s or 2p electron, the electrons in the n = 3 shell make no
contribution, the seven electrons in the same shell contribute 0.35,
and the 1s electrons contribute 0.85 each.
Zeff (2s/2p) = 14 − (7 x 0.35) − (2 x 0.85) = 9.85
The 2s and 2p feel a significant part of the nuclear charge.
CHEM 101
Slater's rules
For the 3s and 3p the calculation is.
Zeff (3s/3p) = 14 − (3 x 0.35) − (8 x 0.85) − (2 x 1.0) = 4.15
Effective nuclear charge Effective nuclear charge
Silicon Carbon
Zeff (1s) = 13.7 Zeff (1s) = 5.7
Zeff (2s/2p) = 9.85 Zeff (2s/2p) = 3.25
Zeff (3s/3p) = 4.15

Compare the Zeff for the valence electrons of Carbon and Silicon i.e.
elements in the same group of the periodic table.
Conclusion
➢ Zeff is higher for 3s and 3p in Si than for 2s and 2p in C.
CHEM 101
Slater's rules
Q: Use Slater's rules to calculate the effective nuclear charge as
experienced by the 1s, 2s or 2p, 3s or 3p electrons in chlorine.

Q: Explain why Slater's rules predicts Zeff(4s) to rise slowly on

moving across the periodic table from Sc to Zn whereas Zeff (3d) rises
more quickly.
CHEM 101 Einstein's theory of relativity

Einstein's theory of relativity states that the mass mrel of an object

moving at velocity v is related to its rest mass mrest by.
𝑚 𝑟𝑒𝑠𝑡
mrel =
𝑣 2
1−
𝑐

where c is the speed of light.

The mass mrel of an object increases as its velocity v increases.

➢ According to the theory of relativity, mass of electron is

not actually constant but varies with the speed of the
electron.

➢ How does the speed of electron vary in different elements?

 CHEM 101 Speed of electron in various elements

𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑬𝒍𝒆𝒄𝒕𝒓𝒐𝒏 ∝ 𝒁
𝒄
𝑺𝒑𝒆𝒆𝒅 𝒐𝒇 𝑬𝒍𝒆𝒄𝒕𝒓𝒐𝒏 = 𝒁 ×
137
where c is the speed of light and Z is the nuclear charge.
In hydrogen, Z = 1, and the speed at which the electron moves in the
1s orbital is about 1/137 times the speed of light.
speed of light
speed at which the electron moves in H atom = 𝟏 ×
𝟏𝟑𝟕
Increasing the nuclear charge increases the speed at which the
electron moves.
Speed of valence electron in mercury?
speed of electron in mercury (Z = 80) = 80 x c/137 = 0.58 x c
i.e. with increase in nuclear charge Z, the speed of electron increases
CHEM 101 The relativistic mass of the electron

Einstein's theory of relativity states that the mass mrel of an object

moving at velocity v is related to its rest mass mrest by.
𝑚 𝑟𝑒𝑠𝑡
mrel = where c is the speed of light.
𝑣 2
1−
𝑐
➢ Using this equation, we calculate that the electron in the 1s orbital
of a hydrogen atom has a relativistic mass of only 1.00003 times
the rest mass.
➢ However, for a heavier element such as mercury (Z = 80) the
velocity of the 1s electron is approximately 80/137 or 58% of the
speed of light, and so in this case the mass of the electron is 1.23
times the rest mass.

How does the increase in relative mass effects 

Z 2
HR
En = − 2
the energy. n
CHEM 101 Relativistic effects in the heavy elements

A further contribution to the increased Zeff felt by the 6s electrons (or,

equivalently, to the lowering of their energy) is due to relativistic
effects.
In order to understand this, we need to look back at the equation for
the energy, En, of an electron in a one-electron system in an orbital
with principal quantum number n
2 𝑍 2 𝑚 𝑒 𝑒4
E n = − H 2
Z R
𝐸𝑛 = −𝑅𝐻 × 2 𝑅𝐻 =
n 𝑛 8𝜀02ℎ2
Whilst this relationship is most conveniently written using the
Rydberg constant, RH, this constant is just a collection of the other
fundamental constants. The equation may be rewritten in terms of
these fundamental constants as
𝑚𝑒𝑒4 𝑍2 where me is the mass of the electron, e is the charge
𝐸𝑛 = − 2 2 × 2 on the electron, Ɛo is the vacuum permittivity, and h is
8𝜀 0 ℎ 𝑛 Planck's constant.
CHEM 101 Relativistic effects in the heavy elements

𝑚𝑒𝑒4 𝑍2
𝐸𝑛 = − 2 2 × 2
8𝜀 0 ℎ 𝑛

➢ The important point is that the orbital energy depends on the mass
of the electron, me.
➢ According to the theory of relativity, this mass is not actually
constant but varies with the speed of the electron.
➢ In heavier element such as mercury (Z = 80) the velocity of the 1s
electron is approximately 80/137 or 58% of the speed of light, and
so in this case the mass of the electron is 1.23 times the rest mass.
➢ Taking into account this increase in the mass, the relativistic
energy of the 1s electron in mercury is lower than would otherwise
be predicted.
CHEM 101 The relativistic mass of the electron

It is not just the orbital energy which is affected by 𝜺 𝒉𝟐

the mass of the electron. The expression for the Bohr a0 =
𝟎
𝒎𝒆𝝅𝒆𝟐𝒁
radius also includes the mass of the electron
Therefore, the relativistic increase in the mass causes ao to decrease
and hence the orbital to contract. The same contraction occurs in
other orbitals for which relativistic effects are significant.
➢ As the wavefunction for an s orbital is non-zero at the nucleus,
electrons in s orbitals experience the effects of the nuclear charge
more than electrons in other orbitals. Consequently, relativistic
effects are most significant for s electrons in the heavier atoms.
➢ Furthermore, since the s electrons are most effective in shielding
the other electrons in the atom, their being closer to the nucleus
shields the other electrons more than would otherwise be expected
leading to a notable expansion of the valence d and f orbitals.
CHEM 101 Relativistic effects in the heavy elements

➢ The energies of electrons can be affected by relativistic effects.

➢ It is really only the heavy elements for which these effects are really
Significant.
➢ Relativistic effects provide an explanation for some of the
anomalous properties of these heavy elements.
CHEM 101 Why gold is colored while other metals are not?

E E

6s 6s relativistic
Absorbs and
emits in UV
region Absorbs and
emits in Visible
region

5d 5d

➢ The contraction of the 6s orbital makes gold have the highest

electronegativity among all metals (2.54) and enhances its trend to
present a negative oxidation state.
CHEM 101 Why Mercury is liquid while Zn & Cd solid?

Without relativistic With relativistic

E E

6s 6s

5d 5d
Melting point generally increases down the group. Due to relativistic effect, 6s electrons in
mercury experience greater pull from the nucleus. Furthermore, 6s orbital of mercury being
fully filled has limited inherent reactivity. This additional pull on 6s electrons in mercury,
because of relativistic effect, results in further curtailing of its reactivity. 6s electrons in
mercury therefore can not engage in forging stronger bonding with each other, hence results
in liquid state instead of solid as is the case with all other metals.
CHEM 101 Atomic sizes across the periodic table

➢ The following Figure

shows the observed radii
of the elements in the form
of a three dimensional
periodic table. 𝑎0 𝑛 2
𝑟=
𝑍𝑒𝑓𝑓
➢ For a given period, the atomic radii are at a maximum for the
Group 1 metals, and then decrease steadily across the period,
reaching a minimum at Group 18. (will discuss TM later).
➢ This steady decrease we can attribute to the increase in Zeff across
a period.
➢ On moving down a group, the effect of increasing n is dominant
over the effect of the increase in Zeff which leads to an increase in
the size.
 𝑎0 𝑛 2
CHEM 101 Decreasing radii of the heavier elements 𝑟 =
𝑍𝑒𝑓𝑓
➢ With the effects of n2 and Zeff opposing one another, it would be
difficult to predict exactly how the size might change on
descending a group.
➢ For instance, it turns out that the third row transition metals are
approximately the same size as the second row.
➢ For these elements, the increase in n2 must be more or less
balanced by the increase in Zeff together with a relativistic
contraction of the outermost 6s orbital.
 𝑎0 𝑛 2
CHEM 101 Decreasing radii of the heavier elements 𝑟 =
𝑍𝑒𝑓𝑓
➢ Relativistic effects become more and more important as we
descend a group, and these effects result in the very heaviest
members of some groups actually being smaller than the previous
members.
➢ Consider the data for Group 2, as an example

➢ We can explain the fact that radium is actually smaller than barium
as being due to the greater value of Zeff for radium, together with a
contribution from relativistic effects as mentioned above.
CHEM 101 Size, overlap and bond strengths

➢ It is important to understand how the size of orbitals vary across

the periodic table since the size plays an important role in
determining bond strengths.
➢ The crucial point is that overlap of smaller valence orbitals tends
to give stronger bonds than the overlap of larger orbitals.
➢ The observed bond strengths for Group 1 diatomic molecules in
the gas phase are

➢ As we descend the group, the increased repulsion due to the 'core'

electrons (the electrons other than the valence electrons) means
the atoms cannot approach each other sufficiently well to achieve
the same degree of overlap as is possible for the lighter atoms.
Overlap decreases down the group
CHEM 101 Ionization Energies

Ionization energy is the minimum amount of energy required to

remove the most loosely bound electron, the valence electron, of an
isolated neutral gaseous atom or molecule.

H(g) → H+(g) + e−

➢ The energy required to ionize an atom is reasonably well

approximated by minus the energy of the orbital from which the
electron is being removed.

IE = − Orbital energy

➢ The trends we have seen in the effective nuclear charges may also
therefore be used to understand the trends in ionization energies
(IE).
CHEM 101 Trend in Ionization Energies

➢ The IE generally increase on moving across a period due to the

increasing Zeff .
➢ The decrease in the IE on going from nitrogen to oxygen is due to
the effects of the exchange interaction.
CHEM 101 Trend in Ionization Energies

➢ On descending a group,
even though Zeff continues
to increase, the ionization
energies decrease due to
the fact that electrons are
being removed from shells
with higher principal
quantum numbers.

➢ However, this decrease in IE begins to level off, and for some

groups the IE may even begin to increase again.
➢ The IE of the third row transition metals, in which the 6s electron
is removed, are all greater than those of the second row due to the
increase in Zeff after filling the f-block, and also due to relativistic
effects.
CHEM 101 The second period anomaly

The following Figure shows

how the average ionization
energy for successively
removing the valence electrons
varies on moving down
Groups 13, 14, and 15.
For each group, the average IE of the first member (i.e. boron,
carbon, and nitrogen) is considerably greater than for the remaining
group members.
The large (average) ionization energies for the first members of each
group mean that these elements are unlikely to form positive ions
and hence compounds with considerable ionic character.
Why? IE of the first member (i.e. boron, carbon, and nitrogen) is
considerably greater than for the remaining group members
CHEM 101 The second period anomaly

The ionization energies of boron, carbon,

and nitrogen are large since their
orbital energies are relatively low.
Small n value resulting in large
negative orbital energies
• IE = − Orbital energy

The orbital energies will be better matched with those of

electronegative elements such as oxygen or fluorine.
The closer the match in orbital energy, the more covalent the bonding
CHEM 101 Electron affinities

The change in energy (in kJ/mole) of a neutral atom (in the gaseous
phase) when an electron is added to the atom to form a negative ion.

For most elements, this process is exothermic.

Electron affinity can also be defined as minus the electron attachment

enthalpy.
The more positive the electron affinity, therefore, the more favorable
energetically it is for the electron to be attached to the atom.
Electron affinities (EA) are notoriously difficult to measure
experimentally and as a result are often determined by indirect
methods. There is certainly a large degree of error in most values
quoted.
CHEM 101 Electron affinities

The above Figure shows a set of values and how they vary across the
periodic table.
The general trends may be understood by
➢ considering how the relevant orbital energies vary, and by
➢ considering the electron configurations of the elements.
CHEM 101 Electron Affinities: Filled and half-filled shells

Trying to add an extra electron to an atom with a filled shell or filled

subshell is not favorable.
In the case of the elements from Group 18, the extra electron would
have to be added to a higher energy orbital starting a new shell. This
is particularly unfavorable, and so the EA for all the noble gases are
negative.
The elements of Group 2 all have
a filled s orbital and so the extra
electron would have to be
accommodated in a p orbital,
which as we have seen, is slightly
higher in energy. This results in Elements in Group 7 and 15 have
the EA for these elements being lower electron affinities than
small or negative. those in groups on either side.
Dr. GhayoorAbbas
CHEM 101 The influence of the effective nuclear charge

Ignoring the special cases of elements with filled and half-filled

subshells, there is a general increase in EA across a period.
This is due to the lowering in energy of the orbital into which the
added electron is accommodated.
Because the electrons added to energy levels become closer to the
nucleus, thus a stronger attraction between the nucleus and its
electrons.
Remember that greater the
distance, the less of an
attraction; thus, less
energy is released when
an electron is added to the
outside orbital.
Halogens, have the largest electron affinities.
Chapter 8: Keeler
CHEM 101 The influence of the effective nuclear charge

➢ After the halogens, the element with the next largest EA is gold.
➢ This can be understood by recalling that the electronic
configuration of gold ([Xe]6s15d10) has a filled d subshell but a
vacancy in the 6s shell.
The energy of the 6s orbital for the third row transition metals is
lowered due to the large Zeff and relativistic effects.
Gold is the element that has
the 6s orbital lowest in
energy and still able to
accommodate an extra
electron.
The auride ion, Au−, has
been detected in a number of
salt-like compounds.
Chapter 8: Keeler
CHEM 101 Electron Affinities: Moving down a Group

➢ Electron affinity decreases down the groups and from right to left
across the periods on the periodic table because the electrons are
placed in a higher energy level far from the nucleus, thus a
decrease from its pull.
➢ As one goes down the period, the shielding effect increases, thus
repulsion occurs between the electrons. This is why the attraction
between the electron and the nucleus decreases as one goes down
the group in the periodic table.
Anomaly: Electron affinities
for the p-block elements in
Period 2 are all less than the
values for the corresponding
elements in the same group
from Period 3.Why?
Chapter 8: Keeler
CHEM 101 Electron Affinities: The second period anomaly

Anomaly: Electron affinities

for the p-block elements in
Period 2 are all less than the
values for the corresponding
elements in the same group
from Period 3.
Why?
➢ The reason for the low electron affinities for the Period 2 elements
has been put down to their small sizes.
➢ As we have already seen, these elements are particularly small,
fluorine especially so.
➢ Adding an extra electron results in more electron-electron
repulsion than is the case for the larger atoms, and it is this that
results in their small electron affinities.
Chapter 8: Keeler
 Acknowledgment
Associate Professor Dr. Ghayoor Abbas Chotana

& Associate Professor Dr. Habib ur Rehman

Department of Chemistry & Chemical Engineering

SBA School of Science & Engineering LUMS