Slaters rules

- provides estimates of the Effective nuclear charges, Zeff,

experienced by electrons in different atomic orbitals.
- based on experimental ionization energies

Zeff = Z - S
where Z = nuclear charge,
Zeff = effective nuclear charge,
S = screening (or shielding) constant

Values of S may be estimated as follows:

1. Write out the electronic configuration of the
element in the following order and groupings:
(1s), (2s, 2p), (3s, 3p), (3d ), (4s, 4p), (4d ), (4f ), (5s, 5p) etc.

2. Electrons in any group higher in this sequence than

the electron under consideration contribute
nothing to S.
3. Consider a particular electron in an ns or np orbital:
(i) Each of the other electrons in the (ns, np)
group contributes S = 0.35.
(ii) Each of the electrons in the (n - 1) shell
contributes S = 0.85.
(iii) Each of the electrons in the (n - 2) or lower
shells
contributes S = 1.00.

4. Consider a particular electron in an nd or nf orbital:

(i) Each of the other electrons in the (nd, nf ) group
contributes S = 0.35.
(ii) Each of the electrons in a lower group than the
one being considered contributes S = 1.00.
- shielding is ns, np is 100% effective; s and p more penetrating

Application of Slaters rules

Confirm that the experimentally observed electronic
configuration of K, 1s2 2s2 2p6 3s2 3p6 4s1, is
energetically more stable than the configuration 1s2
2s2 2p6 3s2 3p6 3d1.

For K, Z =19
The effective nuclear charge experienced by the 4s
electron for the configuration 1s2 2s2 2p6 3s2 3p6 4s1 is:
Zeff = Z - S
= 19 - [(8 x 0.85) + (10 x 1.00)]
= 2.20
For the configuration 1s2 2s2 2p6 3s2 3p6 3d1 is:
Zeff = Z - S
= 19 - (18 x 1.00)
= 1.00
Thus, in the ground state of potassium, it is the 4s atomic orbital
(which feels greater Zeff, more stable) that is occupied.

Electronic Configurations
Lanthanides and Actinides

of

Transition

Metals,

including

Solid lines surrounding elements designate filled or half-filled d or f subshells.

Dashed lines surrounding elements designate irregularities in orbital filling.

Schematic Energy Levels

for Transition Elements (TE)
a) Schematic interpretation of
electronic configurations for
TE in terms of interorbital
repulsion and trend in
subshell energies.
b) A similar diagram for ions

Ex. Cr: 4s1 3d5 not 4s2 3d4

The diagram shows that s

electrons are removed before
d electrons.
The electrons with highest n are
always removed first in the
formation of ions from the transition
elements.

Ex. Sc+: 4s1 3d1 not 4s2

Exercises:
1. Use Slaters rules to estimate values of Zeff for (a) a 4s and (b)
a 3d electron in a V atom.
2. Based on Zeff values, which is the possible valence
configuration of the ground state of a V+ ion, 3d3 4s1 or 3d2
4s2.
3. Based on the schematic E level below, what is the electronic
configuration of Fe+ and V+.

Formation of a positive ion by

removal of an electron
reduces the overall electron
repulsion and lowers the
energy of the d orbitals more
than that of the s orbitals

Ionization energies, IE
The first ionization energy, IE1, of an atom is the internal energy
change at 0 K, !U(0 K), associated with the removal of the first
valence electron in the gas phase.
X(g) " X+(g) + e

The second ionization energy, IE2 is based on the equation

X+(g) " X+2(g) + e

Apparent repeating patterns and some features of IEs:

- the high values of IE1 associated with the noble gases
- the very low values of IE1 associated with the group 1 elements
- the general increase in values of IE1 as a given period is
crossed

- the discontinuity in values of IE1 on going from an element in

group 15 to its neighbour in group 16
- the decrease in values of IE1 on going from an element in
group 2 or 12 to its neighbour in group 3 or 13
- the rather similar values of IE1 for a given row of d-block
elements.
mino

ma
jor c
h

ang

r ch

ang

The break in the trend at B is attributed to occupation of new p

orbital that has most of its electron density farther away from the
nucleus than the other electrons.
Its easier to remove a 2p electron in B than 2s2 electrons of Be..
At the fourth p electron, at O, a similar drop in ionization energy
occurs.
The new (8th) electron shares an orbital with one of the previous
2p electrons.

The pairing energy, or repulsion between two electrons in the

same region of space, reduces the ionization energy.

Filled and half-filled shells are often referred to as possessing a

special stability.
The key is actually the exchange energy, K!
Consider two electrons in different orbitals.
The repulsion between the electrons if they have anti parallel
spins is greater than if they have parallel spins
e.g. for a p2 configuration:
versus
The difference in energy between these two configurations is the
exchange energy, K
i.e. this is the extra stability that the right-hand configuration has

The total exchange energy, #e is expressed in terms of K

"e = $

N(N #1)
K
2

where N = number of electrons with parallel spin

!
Electron affinities
The first electron affinity (EA1) is minus the internal energy
change (EA = -!U) for the gain of an electron by a gaseous
atom.
Y(g) + e " Y-(g)
The second electron affinity of atom Y is defined for process
Y-(g) + e " Y-2(g)

The attachment of an electron to an atom is usually exothermic.

Repulsive interactions are dominant when an electron is added
to an anion and the process is endothermic

The pattern of electron affinities with changing Z is similar to

that of the IEs, but with smaller absolute numbers.
- electron removal from a (-) ion (opposite for EA) is easier than
removal from a neutral atom (IE).

The noble gases have smallest EAs.

Covalent and Ionic Radii (Size)

Opposing factors:
As the nuclear charge increases, the electrons are pulled in
toward the center of the atom, and the size of any particular
orbital (thus the size of atom) decreases.
On the other hand, as the nuclear charge increases, more
electrons are added to the atom and their mutual repulsion keeps
the outer orbitals large.
The interaction of these two effects results in a gradual decrease
in atomic size across each period.

Crystal Radii for Selected Ions

Z

Element

Radius (pm)

Alkali metal ions

3
11
19
37
55

Li+
Na+
K+
Rb+
Cs+

90
116
152
166
181

Alkaline earth ions

4
12
20
38
56

Be2+
Mg2+
Ca2+
Sr2+
Ba2+

59
86
114
132
149

Other cations

13
30

Al3+
Zn2+

68
88

Halide ions

9
17
35
53

FClBrI-

119
167
182
206

Other anions

8
16

O2S2-

126
170

Anions are generally larger than cations with similar numbers of electrons (Fand Na+ differ only in nuclear charge, but the radius of fluoride is 37% larger)

Crystal Radius and Nuclear Charge

Ion

Protons

Electrons

Radius (pm)

O2-

10

126

F-

10

119

Na+

11

10

116

Mg2+

12

10

86

Crystal Radius and Total Number of Electrons

Ion

Protons

Electrons

Radius (pm)

O2-

10

126

S2-

16

18

170

Se2-

34

36

184

Te2-

52

54

207

Crystal Radius and Ionic Charge

Ion

Protons

Electrons

Radius (pm)

Ti2+

22

20

100

Ti3+

22

19

81

Ti4+

22

18

75

The radius decreases as nuclear

charge increases for ions with
the same electronic structure,
such as O2-, F-, Na+, and Mg+2,
with a much larger change for
the cations.

Within a family, the ionic radius

increases as Z increases because
of the larger number of electrons
in the ions and, for the same
element, the radius decreases
with increasing charge on the
cation.