CHEM2643

The Electronic Structure of Atoms

Fig. 2-9
Relative energies of atomic
orbitals as a function of
atomic number

Use experimental data to

arrange atomic orbitals
in correct energy order
for building up of
electronic structures of
atoms.
Fig 2-10
The order in which
atomic orbitals are used
in building up the
electron configuration

p-orbitals:
threefold
degeneracy

d-orbitals:
fivefold degeneracy

f-orbitals:
sevenfold
degeneracy
Understand the reasons for the energy ordering.

 Repulsions among electrons

 Relative amplitudes of the radial portions of the

atomic orbital wave functions - compare the
extent to which the radial portions of the various
wave functions penetrate to the nucleus
Radial penetration of the wave functions

An electron in an atomic orbital with electron density

close to the nucleus is stabilized by close interaction
with the positive charge of the nucleus.

Evaluate the stability of an electron by comparing the

radial electron density functions.
For any n: s-orbital most electron density close to the
nucleus, then p, d, f.

Order of stability: s > p > d > f

Ordering presented in Fig. 2-10

Fig. 2-9: crossing of ns and (n-1)d energy levels

Electron configurations

Aufbau principle - build up from the bottom

- orbitals of lowest energy first

Hund’s rule - where orbitals are available in degenerate

sets, maximum spin multiplicity preserved
(electrons are not paired until each orbital
in a degenerate set is half-filled)

Pauli exclusion principle - no two electrons may have the

same set of 4 quantum numbers
- two electrons in the same orbital
must have opposite signs,
ms = +½ and ms = −½
- maximum 2 electrons per orbital
Be able to fill orbitals from Z = 1 to Z = 86 (Rn)

Know the names of these elements.

Period 1 Period 2

Period 3 Period 4
Period 5
Period 4 started with 4s, then 3d and ended with 4p
Period 5 follow same pattern for its 18 elements:
Period 5 starts with 5s, then 4d and ends with 5p.

Period 6
Consists of 32 elements from 55Cs to 86Rn.
6s is filled from 55Cs to 56Ba.
5d starts to fill with 57La, but this gets interrupted –
from 58Ce to 71Lu (14 elements) the f-orbital gets filled.
Filling of d-orbitals is resumed with 72Hf.

58 Ce: [Xe] 6s25d04f2, 71 Lu: [Xe] 6s25d14f14

72 Hf: [Xe] 6s25d24f14

Exceptions
24 Cr: [Ar] 4s 1
3d5
(not [Ar] 4s 2
3d4
)

29 Cu: [Ar] 4s13d10 (not [Ar] 4s23d9)

42 Mo: [Kr] 5s14d5 (not [Kr] 5s24d4)

47 Ag: [Kr] 5s 1
4d10
(not [Kr] 5s 2
4d9
)

41 Nb: [Kr] 5s 1
4d4
(not [Kr] 5s 2
4d3
)

44 Ru: [Kr] 5s14d7 (not [Kr] 5s24d6)

45 Rh: [Kr] 5s 1
4d8
(not [Kr] 5s 2
4d9
)

46 Pd: [Kr] 5s04d10 (not [Kr] 5s24d8)

57 La: [Xe] 6s 2
5d1
(not [Xe] 6s 4f )
2 1

64 Gd: [Xe] 6s25d14f7 (not [Xe] 6s25d04f8)

78 Pt: [Xe] 6s15d9 (not [Xe] 6s25d8)

79 Au: [Xe] 6s 1
5d10
(not [Xe] 6s 2
5d9
)
Write the electron configuration of 82Pb
Write the electron configuration of 82Pb

1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2

or

[Xe] 6s24f145d106p2
The periodic table

http://www.rsc.org/periodic-table

http://elements.wlonk.com/
http://www.chemicool.com/images/periodic-table.png
Search for arrangement of the elements
Group together similar chemical properties
Logical sequence
Increasing atomic weights
Mendeleev
Arranged in horizontal rows
Related elements in vertical columns
Moseley
Proper sequence: atomic number
Vertical columns contain chemically similar elements
and electronically similar atoms
Periodic arrangement of electron configurations give the
same result as what Mendeleev deduced from chemical
observations.
Numbering of vertical columns (groups)
Traditional: Roman numerals (I to VIII) with A or B
IUPAC: Arabic numerals (1 to 18)

Noble gases
Group VIIIA, ns2np6 (except He: 1s2)
He, Ne, Ar, Kr, Xe, Rn
Alkali metals
Group IA, ns1
Form +1 cations
Li, Na, K, Rb, Cs, Fr
Alkaline earth metals
Group IIA, ns2
Form +2 cations
Be, Mg, Ca, Sr, Ba, Ra
Halogens
Group VIIA, ns2np5
Form −1 anions
F, Cl, Br, I, At
Chalcogens
Group VIA, ns2np4
Form −2 anions
O, S, Se, Te, Po
Pnictogens
Group VA, ns2np3
N, P, As, Sb, Bi
Group IVA, ns2np2
C, Si, Ge, Sn, Pb

Group IIIA, ns2np1

B, Al, Ga, In, Tl
Main group elements
Outer shells: s and p electrons

s-block, p-block, d-block elements

d-block (transition elements)

Incomplete set of d electrons
1st, 2nd, 3rd transition series
Zn, Cd, Hg
Maximum oxidation state +2
f-block elements
Lanthanides: 4f orbitals
Actinides: 5f orbitals
Hund’s rule (p55)
1. Electrons make use of different orbitals as far as
possible (within a set of degenerate orbitals)
A consequence of the charge of the electrons –
electrons minimise repulsive forces by occupying
different p orbitals
2. Parallel spins (same value of ms) are used until the
Pauli exclusion principle requires pairing of spins
Early pairing of spins leads to less stable arrangements
Most stable electronic state: the state with maximum spin
multiplicity (largest number of unpaired electron spins).
Hund’s rule implies:

1. Spreading out of electrons as wide as possible

in the space surrounding the nucleus

2. This spreading of electron density leads to

extra stability

How does this stability arises?

The effective nuclear charge (Z*) which is felt by an
electron is not the actual charge Z of the nucleus of the
atom (JC Slater). The amount of nuclear charge felt by an
electron depends on:

1. The type of orbital in which the electron is housed

2. The ability of other electrons in more penetrating

orbitals to screen (or shield) the electron from the
nucleus

An electron will occupy an available orbital where the

nucleus is most effective at offering positive charge to
stabilize the electron.
Any orbital that places appreciable electron density
between the nucleus and a second orbital is said to
penetrate the region of space occupied by the
second orbital.

The electron is more stable in the more penetrating

orbital (why?)

The extent to which orbitals penetrate electron

clouds of other orbitals is s > p > d > f.

An electron will experience the greatest effective

nuclear charge when housed in an s orbital (for any
given n), then p, etc. (Reason for Aufbau)
Geometry and orientation of the p orbitals makes them
poor at shielding one another from the nucleus.

From B to Ne, each new electron experiences a new and

different effective nuclear charge.
At B, electron goes into 2px
At C, the new electron goes into 2py
(perpendicular to 2px)
2py poorly screened from the nucleus by 2px
Effective nuclear charge for last electron of C is
higher than that for B.

At N, the electron goes into 2pz – effective nuclear

charge of last electron even higher
(2pz perpendicular to previous two)
Where screening of an electron is poor, the effective
nuclear charge is high.

In terms of Hund’s rule: Electrons spread out into a

degenerate set of orbitals in order to experience the
maximum effective nuclear charge.
Slater’s screening constant, σ

Slater proposed an empirical constant that

represents the cumulative extent to which the other
electrons of an atom shield (or screen) any particular
electron from the nuclear charge.

Z* = Z − σ

Z* is always smaller than Z (the electron is screened

or shielded from Z by an amount σ).

The value of σ for the electron in question is the

cumulative total provided by the other electrons of
the atom – calculated using Slater’s rules.
Slater’s rules

For an electron in an s or p orbital

1. All electrons in principal shells higher than the
electron in question contribute zero to σ.
2. Each electron in the same principal shell
contributes 0.35 to σ.
3. Electrons in the n-1 shell contribute 0.85 to σ.
4. Electrons in deeper shells contribute 1.00 to σ.
For an electron in a d or f orbital
1. All electrons in principal shells higher than the
electron in question contribute zero to σ.
2. Each electron in the same orbital (i.e. d or f)
contributes 0.35 to σ.
3. All other electrons contribute 1.00 to σ.
Application of Slater’s rules

1. Write the electron configuration for the atom

2. Regroup in the following way:

| | | | |
(1s) (2s and 2p) (3s and 3p) [3d] (4s and 4p) [4d] [4f]|
For an electron in an s or p orbital, use the first set of
Slater’s rules.

For an electron in a d or f orbital, use the second set of

Slater’s rules.
Example 1
Calculate Z* for the 4s electron of 19K.

19 K: 1s2 2s2 2p6 3s2 3p6 4s1

| |
Group/regroup: (1s2) (2s22p6) (3s23p6) (4s1)|
n-3 n-2 n-1 n
1.0 1.0 0.85 0.35
Use first set of rules
σ = (0 x 0.35) + (8 x 0.85) + (10 x 1.0)
= 16.8
Z* = Z – σ
= 19 – 16.8
= 2.2
Example 2
Calculate Z* for one of the 4s electrons of 20Ca.

20 Ca: 1s2 2s2 2p6 3s2 3p6 4s2

| | |
Group/regroup: (1s2) (2s22p6) (3s23p6) (4s2)
n-3 n-2 n-1 n
1.0 1.0 0.85 0.35
Use first set of rules
σ = (1 x 0.35) + (8 x 0.85) + (10 x 1.0)
= 17.15
Z* = Z – σ
= 20 – 17.15
= 2.85
Example 3
Calculate Z* for one of the 4s electrons of 28Ni.

28 Ni: 1s2 2s2 2p6 3s2 3p6 4s2 3d8

| | |
Group/regroup: (1s2) (2s22p6) (3s23p6) [3d8] (4s2) |
n-3 n-2 n-1 n-1 n
1.0 1.0 0.85 0.85 0.35
Use first set of rules
σ = (1 x 0.35) + (16 x 0.85) + (10 x 1.0)
= 23.95
Z* = Z – σ
= 28 – 23.95
= 4.05
Example 4
Calculate Z* for one of the 3d electrons of the 28Ni2+ ion.

28 Ni: 1s2 2s2 2p6 3s2 3p6 4s2 3d8

28 Ni2+
: 1s 2
2s 2
2p6
3s 2
3p6
3d8

| | |
Group/regroup: (1s2) (2s22p6) (3s23p6) [3d8]
1.0 1.0 1.0 0.35
Use second set of rules
σ = (7 x 0.35) + (18 x 1.0)
= 20.45
Z* = Z – σ
= 28 – 20.45
= 7.55
Relative energies of 4s and 3d orbitals
To conclude

Z* increase continually from left to right across the rows of

the periodic table because of imperfect shielding.
Periodic trends

Differences in the orbitals that house the electrons are

partly responsible for the periodic trends

1. The different penetrations of the atomic orbitals can

be judged from evaluation of the size of the orbitals
and the orientation of the orbitals
2. Because of the different penetrations and orientations,
orbitals are used in the sequence as discussed earlier.
3. Because of the different penetrations and orientations,
the valence electrons of the atoms experience different

effective nuclear charges.

4. Properties such as first ionization enthalpy also follow
trends that reflect the different electron configurations
Ionization enthalpy

It is the minimum energy needed to remove the

highest energy electron (outermost) from the neutral
atom in the gaseous state.

Li (1s22s1) Li+ (1s2) + e−

Three major trends
1. Maxima occur at the noble gases and the
minima at the alkali metals
2. Ionization enthalpies increase across any
row of the periodic table
3. The increase is not smooth – there are two
well defined jogs in each series
Three major trends
1. Maxima occur at the noble gases and the
minima at the alkali metals
2. Ionization enthalpies increase across
any row of the periodic table
3. The increase is not smooth – there are two
well defined jogs in each series
Three major trends
1. Maxima occur at the noble gases and the
minima at the alkali metals
2. Ionization enthalpies increase across any
row of the periodic table
3. The increase is not smooth – there are
two well defined jogs in each series
1. Maxima occur at the noble gases and the minima
at the alkali metals

The closed-shell configuration of the noble gases are

very stable and resist disruption, either to form bonds or
to become ionized.

There is an electron outside the preceding noble gas

configuration in the alkali metal atoms. This electron is
well shielded from the attraction of the nucleus and is
therefore easy to remove.

Z* of 10Ne outermost electron: 5.85, I.E. = 2080 kJ/mol

Z* of 11Na outermost electron: 2.20, I.E. = 496 kJ/mol
2. Ionization enthalpies increase across any row of the
periodic table, from the alkali metal to the next noble
gas

The effective nuclear charge grows across a row

because of the cumulative effects of imperfect shielding
by orbitals of the same principal quantum number.
As the effective nuclear charge increases, so does the
energy necessary to ionize the atom.
3. The increase is not smooth – there are two well
defined jogs in each series, from Li to Ne and in
the next period from Na to Ar

In each case the ionization enthalpy drops from s2 to s2p1

and again from s2p3 to s2p4
Drops from 4Be (1s2 2s2) to 5B (1s2 2s2 2p1)
The p electrons are less penetrating than s electrons.
The p electrons are more shielded and easier to remove.

The next drop is from 7N (1s2 2s2 2p3) to

8 O (1s 2
2s 2
2p4
)
The 2p shell is half-full at N and each further 2p electron
added enters an orbital already singly occupied. These
electrons are partly repelled by the electron already
present and are thus less tightly bound.
There is also a jog in the first transition series

Cr (4s1 3d5) Cr+ (3d5) + e−

Cu (4s1 3d10) Cu+ (3d10) + e−

The 3d5 and 3d10 configurations are more stable and

the 4s electron is easily removed.
Electronegativity (χ, Chi)
Electronegativity: An empirical measure of the tendency of
an atom in a molecule to attract electrons.
Electron affinity: The energy change for the process of
adding an electron to a neutral atom in the gaseous state
to form a negative ion (enthalpy of electron attachment).
Electronegativity related to electron affinity –
Mulliken: Electronegativities are determined in part by the
tendency of an atom to gain additional electron density and
by its tendency to retain the electron density it already has.
Limitation – electron attachment enthalpies not available
for all elements.
Pauling
If two atoms A and B had the same χ, the strength of the
A-B bond would be equal to the geometric mean of the A-A
and B-B bond energies.

For a majority of A-B bonds the energy exceeds the

geometric average, because atoms have different χ, and
because of an ionic contribution in addition to the covalent
contribution.

Pauling proposed that the “excess” bond energies could be

used to determine electronegativity differences.
Using Pauling to calculate χ of H
Bond energies: H-F: 566, H-H: 436 and F-F: 158 kJ/mol
Geometric mean = (EF-F x EH-H)½
= (158 x 436)½
= 262 kJ/mol
Difference (Δ) = 566 − 262
= 304 kJ/mol

χ A – χB = 0.102 Δ½ (Pauling)

Pauling assigned χ = 4.00 to F

χH = χF − 0.102 Δ½
= 4.00 − 0.102 (304)½
= 2.22
Exercise

Use the Pauling method to calculate the electronegativity

of 14Si using the following single bond energies:
C-Si: 301, C-C: 356, Si-Si: 226 kJ/mol
χC = 2.55 and χC > χSi
Using Pauling to calculate χ of Si
Bond energies: C-Si: 301, C-C: 356, Si-Si: 226 kJ/mol
Geometric mean = (ESi-Si x EC-C)½
= (356 x 226)½
= 283.65 kJ/mol
Difference (Δ) = 301 − 283.65
= 17.35 kJ/mol

χ A – χB = 0.102 Δ½ (Pauling)

χC − χSi = 0.102 Δ½
χSi = χC − 0.102 Δ½
= 2.55 − 0.102 (17.35)½
= 2.125
Allred and Rochow
An atom will attract electron density in a chemical bond
according to Coulomb’s law.

Z* = effective nuclear charge

R = mean covalent radius of electron density in Å.
(Å = pm x 10−2)

Numerical constants chosen to bring the values into

accord with those of Pauling.
Using Allred and Rochow to calculate χ for K

For 19K is Z* = 2.2 and r = 198 pm (198 pm = 1.98Å)

2.2
χK = 0.359 ( 1.982 ) + 0.744
= 0.945
Allen
Electronegativity is the average one-electron ionization
enthalpy of all s and p electrons in the valence shell of
an atom

Most recent electronegativity scale (spectroscopic

electronegativity)

Developed for the main group elements

Allen’s values not substantially different from those of the

others.
 m = number of p electrons
n = number of s electrons
= average one-electron ionization enthalpy of
p electrons
= average one-electron ionization enthalpy of
s electrons

and determined using high resolution spectroscopic

data for each element.
Noble gases – resistance to ionization, high χspec values.

Drawback: cannot be applied to calculate χ of a transition

element
Summary

Metals: low electronegativities

Nonmetals: high values
Metalloids: in between

Atoms with the highest electronegativities are those with

the smallest radii and the highest effective nuclear charges
What is a complex?
Composed of a transition element and ligands, e.g.
[Fe(CN)6]3−, where CN− is the ligand.

More atoms (ligands) bond to the central atom compared to

the demand of ionic charge of the metal e.g. Fe in this
example is Fe3+ and each ligand is CN−.

Fe3+ + 6CN− [Fe(CN)6]3−

Just as the ionic compound FeCl3 forms from Fe3+ and Cl−,
can the salt K3[Fe(CN)6] be formed with the complex
[Fe(CN)6]3− as the anion.
Complexes have a specific geometry due to the
hybridization of the central element e.g. d2sp3 (octahedral)

Ligands alone are responsible for bonding to the central

metal by way of donating 2 electrons to form the bond.

cisplatin
High and low spin complexes

Low spin complex: Valence electrons (d orbital) of

the metal ion are paired to a maximum, in contrast to
Hund’s rule.

High spin complex: Metal ion has the largest number

of unpaired electron spins, according to Hund’s rule.

This classification is not allowed for d0, d1, d9 and d10

metal ions.
Example:
Spectrochemical series

Br− < Cl− < F− < H2O < NH3 < CN− < CO
Weak coordinating Strong coordinating
ligands ligands
High-spin complexes Low-spin complexes

The position of the ligand in the spectrochemical series

determine the geometry of the complex.
18 electron rule for complexes
Exercise - 18 electron rule

Determine if the following complexes comply with the

eighteen electron rule:

1. K2[NiCl4] (16 electrons)

2. [Ni(CO)4] (18 electrons)

3. [Ni(en)3](S2O3) (20 electrons,

“en” = neutral, bidentate)

4. K4[Mo(CN)8] (18 electrons)

1. K2[NiCl4]
[NiCl4]2−, Ni2+
28Ni: [Ar] 3d 4s Ni2+: [Ar] 3d8
8 2
28

Ni: 8 electrons
4 Cl ligands: 4 x 2 = 8 electrons
Sum is 16 electrons

2. [Ni(CO)4]
Ni0
28Ni: [Ar] 3d 4s
8 2

Ni: 10 electrons
4 CO ligands: 4 x 2 = 8 electrons
Sum is 18 electrons
3. [Ni(en)3](S2O3)
[Ni(en)3]2+, Ni2+, (en) ligand neutral bidentate
28Ni: [Ar] 3d 4s 28Ni : [Ar] 3d
8 2 2+ 8

Ni: 8 electrons
3 (en) ligands: 3 x 4 = 12 electrons
Sum is 20 electrons

4. K4[Mo(CN)8]
[Mo(CN)8]4−, Mo4+
42Mo: [Kr] 4d 5s Mo4+: [Kr] 4d2
5 1
42

Mo: 2 electrons
8 CN ligands: 8 x 2 = 16 electrons
Sum is 18 electrons
Magnetic properties of atoms and ions
Paramagnetic: • has one or more unpaired electrons,
• will be attracted into a magnetic field

Diamagnetic: • do not contain unpaired electrons

(all electrons are paired),
• are weakly repelled by a magnetic field.

Magnetic susceptibility:
• a measure of the force exerted by the
magnetic field on a unit mass of the
compound,
• is related to the number of unpaired electrons
per unit weight
Orbital motion of unpaired electrons and the spin of the
unpaired electrons contribute to paramagnetism in an atom.

Measured susceptibility per mol:

• gives an indication of the number of
unpaired electrons present,
• used to calculate the magnetic moment, μ

Diamagnetic effect:
• always present,
• may be estimated from measurements on
similar substances that lack the atom or ion
that has the unpaired electrons
The magnetic moment, due entirely to the spins of n
unpaired electrons on the atom or ion, is given by

s=nx½

s equals the sum of the spins of all the unpaired electrons

The unit for atomic magnetic moments is the Bohr
magneton (BM).
Application

29 Cu: [Ar]3d104s1

29 Cu2+
: [Ar]3d 9

One unpaired electron, expect μ = 1.73 BM

(calculated value)

Observed value for CuSO4·5H2O is 1.95 BM.

Higher value can be attributed to the contribution made

by orbital motion of the electron.
and

MnSO4·4H2O: observed μ = 5.86 BM

25 Mn: [Ar]3d 5
4s2

25 Mn2+: [Ar]3d5

5 unpaired electrons, expect μ = 5.92 BM

Exercise: Calculate the magnetic moment for a low-spin
Mn4+-ion.
Exercise: Calculate the magnetic moment for a low-spin
Mn4+-ion.
Calculate the magnetic moment for the high-spin
complex, K3[Mn(ox)3]·2H2O. (ox-2)
Calculate the magnetic moment for the high-spin
complex, K3[Mn(ox)3]·2H2O. (ox-2)