Chapter

p 6
Electronic Structure of Atoms

Electromagnetic Radiation
• Electromagnetic radiation helps us
understand the structure of atoms. It
describes energy carried through space
and has wave-like characteristics.

• Wavelength (λ): Distance between

corresponding points on adjacent
waves.

Speed of Light
• Electromagnetic radiation travels at the
same velocity: the speed of light (c),
3.00 × 108 m/s.

• The relationship between velocity and

the speed of light is:
c = λν

1
 Frequency
• Frequency (v) is the number of
waves passing a given point per
unit of time. Unit is Hz.
• Long
g λ – low frequency
q y
• Short λ – high frequency

The Electromagnetic Spectrum

Wavelength /m Radiation Type

10-13 – 10-9 Gamma Rays
10-9 – 10-8 X-Rays
X Rays
10-8 – 10-7 Ultra-Violet
10-7 – 10-6 Visible
10-6 – 10-4 Infra-Red
10-4 – 10-3 Microwave
10-1 – 101 Radio

EM Radiation Wavelengths

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 An additional model?
• The wave model doesn’t explain all
radiation such as:

– Black body radiation -how an object can glow

when its temperature increases

– Photoelectric effect – how electrons

are emitted from matter after energy
absorption

– Emission spectra – the intensity of

radiation of each frequency emitted
when heated

Energy Quanitized
• Planck believed that energy was also in packets
called quanta

• Einstein used this to

describe the
photoelectric effect

E = hν
where h is Planck’s constant, 6.626 × 10−34 J.s.

Waves or Particles?
• We can relate the wavelength of
light to the energy in one photon,
or packet, of that light

c = λν
E = hν

3
Interaction of Matter & Light
• Radiation sources
– Monochromatic – radiation at a single
wavelength (laser)

– Continuous – radiation through

g whole array
y
of wavelengths

– Line spectra – line for a

given gas like hydrogen

Hydrogen Line Spectrum

• Balmer realized H line spectrum fit a
simple formula

1 ⎛ 1 1 ⎞
• Rydberg Equation: = RH ⎜⎜ 2 − 2 ⎟⎟
λ ⎝ 1
n n 2 ⎠

• RH = 1.096776 x 107 m-1; n1 & n2 are

quantum number integers n2>n1

• Other elements gave other sets of lines

Bohr’s Model of the Atom

• Thomson’s historical plum pudding
model of the atom, Rutherford’s
additions of protons and finally
Chadwick’s neutrons

• Then Bohr realized electrons are

moving at great speeds within the
atom. Electrons are fixed in orbitals.
Transitions in orbitals describe
absorption and emission of light

4
 Bohr’s Model
1. Electrons in an atom can only occupy certain
orbits (corresponding to certain energies).

2. Electrons in permitted orbits have specific,

“allowed” energies; these energies will not be
radiated from the atom.

3. Energy is only absorbed or emitted in such a

way as to move an electron from one “allowed”
energy state to another; the energy is defined
by
E = hν

Problems Yet Again

• Bohr’s model only worked for atoms
and ions that had a single electron
(hydrogen)

• Positives:
– Energies of electrons in atoms were
quantized and characterized by the principal
quantum number, n

– Energy is involved in moving an electron

from one level to another.

Wave Behavior of Matter

• Particle or wave characteristics question
again?
• De Broglie suggested particles have
wavelike properties
• an electron moving about a nucleus has
associated with it a particular λ which
depends on mass and velocity

h
λ=
mv

5
 The Uncertainty Principle
• Heisenberg showed that the more
precisely the momentum of a particle is
known, the less precisely is its position
known:
h
(Δx) (Δmv) ≥
4π
• In many cases, our uncertainty of the
whereabouts of an electron is greater
than the size of the atom itself!

The Uncertainty Principle

• To see the electron position, we must
probe with radiation and change its
position or velocity or both.

• We can only specify the highest

probability of an electron in an orbital.

Quantum Mechanics
• Schrödinger developed a method to
incorporate both the wave and particle nature
of matter.

• A wave function equation describes the energy

of electrons that are quantized.
q

• The probability of finding an electron in a point

in space (the orbital) is found by the square of
the wave function.

6
 Quantum Numbers
• Solving the wave equation gives a set of
wave functions, or orbitals, and their
corresponding energies.

• Each orbital describes a spatial

distribution of electron density.

• An orbital is described by a set of

quantum numbers.

Principal Quantum Number

• Principal Quantum Number (n)
– Correlates with the average distance
of the electron from the nucleus

– Has values of 1, 2, 3, 4

– Called shells which differ in energy

Azimuthal Quantum Number

• Azimuthal Quantum Number, l
– Correlates with the shape of the orbital
where the electron is found

– Labeled s, pd, d, f and called subshells

– Has values of 0, … n-1

– A set of orbitals with the same values of n

and l are called a subshell

Value of l 0 1 2 3
Type of orbital s p d f

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 Magnetic Quantum Number
• Magnetic Quantum Number, ml
– Correlates with the orientation of the
orbital, each orbital in a subshell points in a
different direction

– Has values of –l,…0,…l

– Therefore, on any given energy level,

there can be up to 1 s orbital, 3 p
orbitals, 5 d orbitals, 7 f orbitals, etc.

Magnetic Quantum Number

• Orbitals with the same value of n form a
shell.

• Different orbital types within a shell are

subshells.
subshells

Orbital Shapes
p
s

8
Hydrogen Orbital Energies
• For a one-electron
hydrogen atom,
orbitals on the same
energy level have the
same energy.

• That is, they are

degenerate.

Orbital Energies
• As the number of
electrons
increases, though,
so does the
repulsion between
them.
them

• Therefore, in
many-electron
atoms, orbitals on
the same energy
level are no longer
degenerate.

Spin Quantum Number, ms

• Spin Quantum Number, ms
– Correlates with the spin of the
electron
– Has values of –1/2, +1/2

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 Pauli Exclusion Principle
• No two electrons in the same atom can
have exactly the same energy.

• For example, no two electrons in the

same atom can have identical sets of
quantum numbers. Only two electrons
can occupy a single orbital and they
must have opposite spin.

Electron Configurations
• Distribution of all electrons in an atom
• Consist of
– Number denoting the energy level
– Letter denoting the type of orbital.
– Superscript denoting the number of
electrons in those orbitals.

Shorthand Notation
• Combinations of the first two quantum
numbers; number of orbital types
equals the shell number (n).
• 1s
• 2s,
2s 2p
• 3s, 3p, 3d
• 4s, 4p, 4d, 4f
• 5s, 5p, 5d, 5f, (5g)
• 6s, 6p, 6d, 6f, (6g, 6h)

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 Orbital Diagrams
• Each box represents one orbital.

• Half-arrows represent the electrons.

• Th
The di
direction
ti off th
the arrow represents
t the
th
spin of the electron.

Hund’s Rule
• For degenerate orbitals, the lowest
energy is attained when the number of
electrons with the same spin is
maximized
• Place 1 electron in each orbital before
pairing up electrons in a single orbital.

The Periodic Table

• We fill orbitals in increasing order
of energy.

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 Bohr’s Model
1. Electrons in an atom can only occupy certain
orbits (corresponding to certain energies).

2. Electrons in permitted orbits have specific,

“allowed” energies; these energies will not be
radiated from the atom.

3. Energy is only absorbed or emitted in such a

way as to move an electron from one “allowed”
energy state to another; the energy is defined
by
E = hν

The Uncertainty Principle

• To see the electron position, we must
probe with radiation and change its
position or velocity or both.

• We can only specify the highest

probability of an electron in an orbital.

Quantum Mechanics
• Schrödinger developed a method to
incorporate both the wave and particle nature
of matter.

• A wave function equation describes the energy

of electrons that are quantized.
q

• The probability of finding an electron in a point

in space (the orbital) is found by the square of
the wave function.

12
 Quantum Numbers
• Solving the wave equation gives a set of
wave functions, or orbitals, and their
corresponding energies.

• Each orbital describes a spatial

distribution of electron density.

• An orbital is described by a set of three

quantum numbers.

Quantum number n
• Principal Quantum Number (n)
– Correlates with the average distance
of the electron from the nucleus

Quantum Number, l
– Correlates with the shape of the orbital
where the electron is found

– Labeled s, p, d, f and called subshells

– Has values of 0, … n-1

– A set of orbitals with the same values of n

and l are called a subshell

Value of l 0 1 2 3
Type of orbital s p d f

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 Quantum Number, ml
– Correlates with the orientation (x,y,z)
of the orbital, each orbital in a
subshell points in a different direction

– Has values of –l,…0,…l

–l 0 l

Quantum Number, ms
– Correlates with the spin of the
electron
– Has values of –1/2, +1/2

Quantum Number Summary

2l+1 n2

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 Energy Levels
Electrons
fill the
lowest
energy
levels
first.

Configuration Rules
• Pauli Exclusion Principle - No two
electrons in the same atom can have
exactly the same energy.

• Hund’s
Hund s Rule - For degenerate orbitals,
orbitals
the lowest energy is attained when the
number of electrons with the same spin
is maximized, place 1 electron in each
orbital before pairing up electrons in a
single orbital.

Orbital Diagrams & Configurations

O
8e- 1s 2s 2p

1s2 2s2 2p4

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 Notation

S 16e- 1s2 2s2 2p6 3s2 3p4

Core Electrons Valence Electrons

Shorthand Notation:

S 16e- [Ne] 3s2 3p4

Periodic Patterns
s
p
d (n-1)

f (n-2)

Periodic Pattern Summary

• Period #
– energy level (subtract for d & f)

• A/B Group #
– total # of valence e-

• Column within sublevel block

– # of e- in sublevel

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 Where does notation come from?

1
2
3
4
5
6
7

1st column
1s1 of s-block

1st Period s-block

Shorthand Notation
1

2
3

4
5

– Core e-: Go up one row and over to the

Noble Gas.
– Valence e-: On the next row, fill in the
# of e- in each sublevel.

Example - Germanium

1
2
3
4
5
6
7

[Ar] 4s2 3d10 4p2

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 Energy Stability
1. Full energy level
2. Full sublevel (s, p, d, f)
3. Half-full sublevel
1
2
3
4
5
6
7

Anomalies
• Electron Configuration
Exceptions
– Copper
EXPECT: [Ar] 4s2 3d9

ACTUALLY: [Ar] 4s1 3d10

– Cu gains stability with a full

d-sublevel.

e- Configuration Chart

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 Anomalies

– Chromium
EXPECT: [Ar] 4s2 3d4

ACTUALLY: [Ar] 4s1 3d5

– Cr gains stability with a half-full d-

sublevel.

Anomalies
• Other examples:
• 4d: Nb, Mo, Ru, Rh, Pd, Ag
• 5d: Pt
• 4f: La,
La Ce,
Ce Gd
• 5f: Ac, Th, Pa, U, Np, Cm

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