– ATOMIC STRUCTURE –

Week 1: Modules 1-3

Chapter 7: Sections 7.1 – 7.5

– Characteristics of light, quanta and photons
– Atomic spectra and energy levels.
– Schrödinger and quantum numbers

Chapter 8 & 9: Sections 8.1 – 8.7, 9.2 – 9.5

– Electron spin and electron configurations
– Periodic properties and bonding

FROM COURSE OUTLINE Page 8, Practice on questions:

• Chapter 7: 7.25, 7.33, 7.37, 7.45, 7.69, 7.87, 7.97,
7.114, 7.117.
•
• Chapter 8: 8.16, 8.21, 8.24, 8.39, 8.43, 8.49, 8.61,
8.63, 8.65, 8.81.

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 – ATOMIC STRUCTURE –

MODULE 1
The Nature of light
Schrödinger and Quantum numbers

EMISSION SPECTROSCOPY

When hydrogen gas is heated in a tube it emits light. This light when analyzed through a prism
shows well-defined violet, blue violet green and red lines.

These colors at specific wavelength are emitted when excited electrons fall back from higher
level of energy to lower levels. In this chapter we are exploring the structure of the Atom to
explain this phenomenon.

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 THE NATURE OF LIGHT
 a type of electromagnetic radiation
 fluctuating electric and magnetic fields
 described by a Wavelength, λ (lambda) and a Frequency ν (nu)
(You may have seen frequency defined as “f” in another class.)

Reference: http://acept.la.asu.edu/PiN/rdg/color/color.shtml

The wavelength and the frequency are related by:

c=λ×ν
where "c" is the velocity of light = 3.00×108 ms–1 in a vacuum.
Units: c → m s–1, λ → m, ν → s–1
NOTE: The unit s–1 = 1/s = reciprocal time = "per second" is given the special name
hertz, abbreviated Hz (1 Hz = 1 s–1)

PACKETS OF ENERGY
Max Planck proposed that electromagnetic radiation comes in units of
defined energy, rather than in any arbitrary quantities. Planck called the
unit of light energy the quantum. He was able to determine the following
relationship:
ε=h×ν
where "h" is a universal constant known as Planck's constant (h = 6.63 ×
10–34 J s)

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Excitation by absorption of energy (light or heat) and de-excitation by emission of light:

The movement of electrons from one orbital to another required absorption or emission of
quantised energy.

QUANTUM MECHANICS
In 1926, Erwin Schrödinger set out the general equations describing wave motion for electrons
(and won the Nobel Prize in Physics in 1933). This wave function (ψ) describes the amplitude
of an electron wave at any point in space. The square of the wave function (ψ2)
gives the probability of finding the electron at any point in space and defines
an ORBITAL.
Reference: http://nobelprize.org/physics/laureates/1933/schrodinger-bio.html

Three quantities (n, ℓ, mℓ) called quantum numbers are involved in the wave
equations. A specific set of values for n, ℓ and mℓ, corresponds to an electron ORBITAL.

Example for H the quantum numbers are: n = 1, ℓ = 0, mℓ = 0 and describe the energy of the
electron in the GROUND STATE.

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 QUANTUM NUMBERS
(REFER TO SECTION 7.5 IN TEXT, P. 282):
There are 4 Quantum numbers. We can remember then using the acronym P.A.M.S. 😊😊
PRINCIPAL Quantum Number, n
ANGULAR MOMENTUM (or Azimuthal) Quantum Number, ℓ
MAGNETIC Quantum Number, mℓ
SPIN Quantum Number, ms

1st Quantum Number: PRINCIPAL Quantum Number, n

• represents the MAIN ENERGY LEVEL of an atom's electrons by a number
n: 1, 2, 3, 4, … , etc.
Letter code: K, L, M, N, … , etc. (used in spectroscopy)
• a K-Shell electron is an electron in the shell with quantum number n = 1
• increasing values of n corresponds to increasing values of energy for the electron
• permitted values of n are 1, 2, 3, 4, ..., etc. (by integers)

2nd Quantum Number: ANGULAR MOMENTUM (or Azimuthal) Quantum Number, ℓ

• tells us about the SHAPE of the electron cloud or orbital
• particular electron cloud shapes are associated with particular values of ℓ
ℓ = 0, spherical
ℓ = 1, dumb-bell shaped
ℓ = 2, a variety of shapes – 5 in all.

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 • both number and letter codes are used
ℓ: 0, 1, 2, 3, … , etc.
Letter code: s, p, d, f, … , etc.
• permitted values of ℓ are from 0 to (n – 1)
 if n = 1, ℓ = 0
 if n = 2, ℓ = 0 or 1
 if n = 3, ℓ = 0 or 1 or 2
 if n = 4, ℓ = 0 or 1 or 2 or 3

3rd Quantum Number: MAGNETIC Quantum Number, mℓ

• determines the NUMBER OF PERMITTED ORBITALS in any group
• permitted mℓ values range from –ℓ through zero to +ℓ
 if ℓ = 0, mℓ = 0
 if ℓ = 1, mℓ = –1, 0, or +1

 if ℓ = 2, mℓ = –2, –1, 0, +1 or +2

• mℓ specifies the permitted ORIENTATIONS in space of an electron cloud.

• tells you how many orbital(s) exist in a sub–levels based on the ℓ value.

Refer to Table 7.1 ) for permissible values of quantum number for atomic orbitals.

4th Quantum Number: SPIN Quantum Number, ms

• this quantum number does NOT arise from the Schrödinger equations
(Refer to Figure 8.2 – Stern-Gerlach Experiment.)

• limits the number of spin energies for an electron to two values: +½ and -½

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Summary of Allowed Combinations of Quantum Numbers
Number of Total Number
Shell n ℓ mℓ Subshell Number of Electrons of Electrons
Notation Orbitals in Needed to in Shell
the Subshell Fill Subshell (2n2)
K 1 0 0 1s 1 2 2
2 0 0 2s 1 2
L 2 1 +1,0, –1 2p 3 6 8
3 0 0 3s 1 2
M 3 1 +1,0,–1 3p 3 6 18
3 2 ±2, ±1,0 3d 5 10
4 0 0 4s 1 2
4 1 +1,0, –1 4p 3 6
N 4 2 ±2, ±1,0 4d 5 10 32
4 3 ±3, ±2, ±1, 0 4f 7 14

END OF MODULE 1

PLEASE COMPLETE ACTIVITY 1

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 – ATOMIC STRUCTURE –

MODULE 2
Electronic Structure of The Elements

Each electron is represented by a set of 4 quantum numbers:

n: main energy level; relative distance of the electron from the nucleus.
ℓ: sub-shell & shape of electron cloud. Each orbital of a sub-shell is identical in energy.
mℓ: designates the orientation of the orbital in space and also tells you how many orbitals.
ms: spin of the electron – only two options
You can envisage a set of n, ℓ, mℓ and ms as a unique electron address, specifying the shape, energy
and orientation cloud and the spin of the electron.

Pauli exclusion Principle:

No two electrons can have the same set of all four quantum numbers (three may be the
same, but then the fourth MUST be different.

Hund's Rule of Maximum Multiplicity:

Electrons are distributed in among the orbitals of a sub–shell in such a way
as to yield the maximum number of unpaired electrons

A set of n, ℓ and mℓ specifies an ORBITAL, which can contain up to two electrons

 when an orbital is full (i.e., contains 2 electrons with quantum numbers ms equal to +½
and –½), we call this "spin paired";
 when an orbital contains only one electron, we say this is "unpaired

In general, electrons in orbitals with different values of ℓ, i.e., in different sub-shells, have
different energies which increase with ℓ–value,
i.e., ℓ = 0 < ℓ = 1 < ℓ = 2 < ℓ = 3
s < p < d < f

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The nℓx notation:
e.g. 1s2 (2 electrons in shell with n=1 & ℓ=0), 2s1, 3d7, …

We are now in the position to arrive at the electronic structure of the elements, making use
of the AUFBAU principal developed by Pauli. (Building-up Principle).

AUFBAU PRINCIPLE (BUILDING-UP PRINCIPLE).

 hypothetical process where electron structure is correctly deduced by successive

addition of the electrons, one at a time until no more remain
 orbitals arranged in order of increasing energy
 we assume that each electron occupies the lowest energy level available to it
all orbitals of a given sub-shell have identical energies, (this amounts to an arrangement
by energy sub-shell). Remember to obey Hund’s Rule: maximum number of unpaired
electrons in a sub-shell


Complication:
It is possible, and indeed happens, for a simple orbital of one level (e.g., 4s) to have a lower
energy than a more complicated orbital of a previous level (e.g., 3d), and hence the 3d
energy level is filled after the 4s fills. See below it is easy to figure out.

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Reference: Ebbing Gammons Fig 8-12

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Examples:
Element Atomic Number Electron Configuration Orbital Representation
(Z) 1s 2s 2p
He 2 1s2 ↑↓ __ __ __ __

Li 3 1s22s1 OR [He]2s1 ↑↓ ↑_ __ __ __

C 6 [He]2s22p2 [He] ↑↓ ↑_ ↑_ __

F 9 [He]2s22p5 [He] ↑↓ ↑↓ ↑↓ ↑_

Ne 10 [He]2s22p6 [He] ↑↓ ↑↓ ↑↓ ↑↓

Na 11 1s22s22p63s1 OR [Ne]3s1

Ca 20 [Ar]4s2

[Ar] takes care of 18 electrons

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COMPLICATION
We then start filling the 3d orbital corresponding to the transition metal species the d-shell and s-
shell are very close in energy. BUT….Once we start filling the d-shell, this stabilizes the shell
and it decreases in energy enough so that it falls below the s-shell, i.e., we have in order of
increasing energy: 3d4s NOT 4s3d- see below the two exceptions.

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CONSEQUENCE AND EXAMPLES

Atomic Read from periodic Adjust to

Element Number table Configuration
(Z)
V 23
Fe 26
EXCEPTIONS !!!

Cr 24

Cu 29

ELECTRON CONFIGURATIONS OF IONS

When writing the electron configurations for ions
– first start with the neutral atom
– then adjust the amount of electrons according to the charge of the ion
Na+
Na : 1s22s22p63s1 or [Ne]3s1
Na+ :

Cl–
Cl : 1s22s22p63s23p5 or [Ne]3s23p5
Cl-

Fe2+:
Fe [Ar] 4s23d6 → [Ar] 3d64s2
Fe2+ [Ar] 3d6

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Core Electrons: Those electrons in the inner shells that can be defined by the closest noble
gas [in bracket]

Valence Electrons: Those “outer” electrons that occupy the shells of higher energy than the
core electrons. “Reactive” electrons that will be involved in BONDS. (All other electrons
not in the valence shell are core electrons.)

Valence Shell: Those orbitals in an atom that contain the valence electrons. These orbitals
are involved in BONDING.

C (Z = 6) configuration [He]2s22p2

Fe (Z = 26) configuration is [Ar]3d64s2

END OF MODULE 2

PLEASE COMPLETE ACTIVITY 2

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 – ATOMIC STRUCTURE –

MODULE 3
Magnetic Properties and Periodic Trends

MAGNETIC PROPERTIES

Single electron behaves like a small magnet

1. DIAMAGNETISM: element not attracted or slightly repelled by magnetic fields

Two electrons paired in an orbital, have opposed spins, their magnetic moments are opposite and

tend to cancel out

2. PARAMAGNETISM: element attracted by magnetic fields

Unpaired electrons give rise to paramagnetism as each electron has a magnetic moment

The larger the number of unpaired electrons, the larger the magnetic moment.

PERIODIC TRENDS

Atomic Radius (refer to Figure 8.16 & 8.17):

a. Left to Right in Periodic Table results in decrease in size (same principal shell and
increasing nuclear charge)

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 b. Top to Bottom in Periodic Table results in increase in size (increase in principal shell, n,
as one moves down a group – atom gets fatter and flabbier)

Figure 8.17: Atomic Radii (Ebbing,

General Chemistry)

Ionisation Energy (Refer to Figure 8.18)

a. L to R – ionisation energy increases.
(same principal shell & increasing nuclear charge – note anomalies caused by sub-shell
filling).

b. T to B – ionisation energy decreases. (increase in principal shell, n, electrons further

from nucleus and more easily removed).

Figure 8.18 (Ebbing, General Chemistry)

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Electron Affinity (Refer to Table 8.4)
Electron affinity is the energy released when a neutral atom gains an electron in the gas
phase, e.g., X(g) + e– (g) → X–(g)
It measures the tendency to gain electrons and is large for elements closest to the Noble
gases.

Table 8.4 (Ebbing, General Chemistry)

Size and Charge (Ions vs. atoms) (Refer to Table 9.3)

a. removal of an electron from a neutral atom results in the remaining electrons being more
tightly held, e.g., Na > Na+.

b. addition of an electron to a neutral atom results in the overall attraction of the nucleus for
electrons being decreased so that anion is larger than the atom, e.g., Cl– > Cl

c. For an ISOELECTRONIC series, the radius varies directly as the charge on the atom, i.e.,
O2– > F– > Ne > Na+ > Mg2+ > Al3+ (Refer to Section 9.3)

Electronegativity (Refer to Figure 9.15)

Electronegativity is a scale devised by Linus Pauling to quantify the power an atom has for
attracting the electrons in its covalent bonds with other atoms. Fluorine is the most electronegative
atom!

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 Periodic Table Trends: L to R: electronegativity increases.
T to B: electronegativity decreases.
Examples: Li (1.0) F (4.0)
Cs (0.7) I (2.5)

Figure 9.15 (Ebbing, General Chemistry)

END OF MODULE 3

PLEASE COMPLETE ACTIVITY 3

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