Ch.

7 The Quantum Mechanical

Atom

Brady & Senese, 5th Ed.

Index
7.1. Electromagnetic radiation provides the clue to the electronic
structures of atoms
7.2. Atomic line spectra are evidence that electrons in atoms have
quantized energies
7.3. Electrons have properties of both particles and waves
7.4. Electron spin affects the distribution of electrons among
orbitals in atoms
7.5. The ground state electron configuration is the lowest energy
distribution of electrons among orbitals
7.6. Electron configurations explain the structure of the periodic
table
7.7. Quantum theory predicts the shapes of atomic orbitals
7.8. Atomic properties correlate with an atom's electron
configuration
Light Acts As A Wave
• Wavelength (λ)– the distance light travels to
complete one cycle
• Frequency (ν) – the number of wave cycles in one
second
 units are cycles per second (cps), Hertz (Hz)
 Hz = s-1

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 3
Frequency And Wavelength Are Related
• Note that as the frequency of the wave increases,
the wavelength decreases
• Regardless of the frequency, light travels at the
same speed, c
• c=λ×ν
 the speed of light (c) = 2.99792458 × 108 m/s
• Learning Check: If the frequency of a radio
station is 300. MHz, what is the wavelength in m?
0.999 m

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 4
Radiant Energy Spectrum
high energy, low energy,
short waves long waves

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 5
Photoelectric Effect (Particle Theory Of Light)

• Albert Einstein (1905) E=hν

• Shining light on a clean metal surface may eject
electrons
• There is a threshold level needed to eject the
electrons (a work function specific to the metal)
 Increasing intensity does not cause the effect
 Increasing the frequency of the light does

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 6
Energy And Light Waves

• The energy of a wave is proportional to the wave frequency,

E=hν
 h= Planck’s constant, 6.626 × 10-34 J•s/photon
• Learning Check: Why is ultraviolet light (320 nm) more
penetrating than a red light (700 nm)? Use energies to make
your case. -19
E320 = 6.2×10 J
E700 = 3×10-19 J

Red light UV light

λ λ
6 x 10-9 m 3 x 10-9 m

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 7
Your Turn!

Which is the correct energy associated with a

photon of light with a wavelength of 450 nm?
A. 6.7×10-4 J
B. 4.4×10-19 J
C. 4.4×10-28 J
D. 6.7×105 J
E. none of these

7.1 Electromagnetic radiation provides the clue to the electronic structures of atoms 8
Flame Emission
• Elements exhibit characteristic colors when burned
• The characteristic spectra are also observed when
elements are subject to strong electrical fields as in
gas discharge tubes.

Note that the

light from the
discharge tube is
actually several
different colored
lines as seen on
the surface of the
CD

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 9
Atomic Emission Spectra
• Light emitted by excited atoms is comprised of a few
narrow beams with frequencies characteristic of the
element
• Atomic spectra are unique for each element

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 10
Patterns In Atomic Line Spectra
• For the hydrogen spectrum, a mathematical pattern
was noted and reported using the Balmer-Rydberg
equation
• n1 and n2 are positive integers , where n1 <n2
• Rydberg constant, RH, is an empirical
constant=109,678 cm-1
 If n1=1, lines called “Lyman series”
 If n1=2, called “Balmer series” 1
  RH ( n12  n12 )
 If n1 = 3 called “Paschen series” 1 2

• Emitted light is quantized

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 11
Learning Check
• What is the wavelength, in m, of light observed from
a transition from n=4 to n=2?
1
λ  109678 cm  1 ( 12  12 ) 486.272 m
2 4
• What is n2 if the photon undergoes transition to n=2
and the emitted light has a wavelength of 6505Å?
1 1
6505108cm 1109678cm (  1 )
n=3
22 n 22

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 12
Your Turn!

What energy is expected for the Balmer emission

line that starts at n=5?
A. 2.3×104 J
B. 4.6×10-23 J
C. 4.6×10-21 J
D. None of these 4.6×10-19
hc  1 1 
E  hcR 2  2 
  n n2 
 1 
6.626 10 34 Js 2.998 108 m 1.06978 10 7  1 1 
E    2 2
1 s m 2 5 

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 13
What Does Quantized Mean?

• energy is quantized if only certain discrete

values are allowed
• the presence of discontinuities makes atomic
emission quantized

Continuous (a) and discrete (b)

potential energy of a tortoise.
The potential energy of the
tortoise in (b) is quantized.

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 14
Your Turn!

Which of the following provides quantized musical

tones?
A. A piano
B. A violin
C. A guitar
D. A flute

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 15
 Bohr’s Model Of The Atom
• Electrons move around the nucleus in fixed paths or
orbits much like the planets move around the sun
• Orbit positions, labeled with the integer n, have
specific potential energy
• The lowest energy state of an atom is called the
ground state (an electron with n = 1 for a hydrogen
atom)

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 16
 Absorption And Emission
• Electrons that absorb
energy are raised to a
higher energy level
• A particular frequency
of light is emitted
when an electron falls
to a lower energy level

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 17
Bohr Equation (1913)
• This equation allows the calculation of the energy, E, of
any orbit
• b= Bohr’s constant
• n is the orbit location

b
E   n2
b  2.18 10 18 J

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 18
 Bohr’s Model Predicts Energy Levels
• Bohr’s (theoretical) equation explains the
experimental (empirical) Rydberg equation
• The combination of constants, b/hc, has a value
which differs from the experimentally derived value
of RH by only 0.05%!

E  Eh  El  ( n b2  n b2 )
 
h l

b 1
 n12 with nh  nl
 
nl2 h

 hc 1  or 1
  b 1
hc nl2  n12
h

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 19
Your Turn!

Which energy is not possible according to Bohr’s

Model?
A. -5.5×10-19 J
B. -1.4×10-19 J
C. -1.8×10-19 J
D. none of these

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 20
 Bohr’s Model Fails
• Theory was not
able to explain
the spectra of
atoms with more
than one electron
• Theory doesn’t
explain the
collapsing atom
paradox

7.2 Atomic line spectra are evidence that electrons in atoms have quantized energies 21
Light Exhibits Interference

• Constructive interference: waves “in-phase”

create waves of greater amplitude ( they add)
• Destructive interference: waves “out-of-phase”
create waves of lower amplitude (they cancel out)

7.3 Electrons have properties of both particles and waves 22

Diffraction And Electrons
• Light exhibits interference, and it also has particle
nature
• Electrons, known to be particles, also demonstrate
interference

7.3 Electrons have properties of both particles and waves 23

Your Turn!

Which of the following is evidence that the

electrons in an atom act as a wave ?
A. the emission spectrum is quantized
B. electrons cannot collapse into the nucleus
C. electrons diffract
D. none of these

7.3 Electrons have properties of both particles and waves 24

Standing vs. Traveling Waves
• Wind produces traveling
waves on the surfaces of
lakes and oceans
• A standing wave is
produced when a guitar
string is plucked: the
center of the string
vibrates, but the ends
remain fixed

7.3 Electrons have properties of both particles and waves 25

Standing Waves
• The waves created by guitar strings are those for which
a half-wavelength is repeated exactly a whole number
of times
• For a strength of length L with n, an integer, this can be


written as:
Ln λ or rearrangin g : λ  2L
2 n
• Wavelengths are quantized!

7.3 Electrons have properties of both particles and waves 26

Three Models of an Electron

a) Bead on a wire
E=½ mv2
b) Standing wave on a
wire λ=2L/n
c) Electron on a wire

E n 2h2
8mL2

7.3 Electrons have properties of both particles and waves 27

The Electron On A Wire- Uniting The Theories
• Particle: the kinetic energy of the moving electron
is E=½ mv2
• Standing wave, the half-wavelength must occur
an integer number of times along the wire’s
length n(λ/2)=L
• de Broglie’s equation provides the link between
these.
 m=mass of particle
h
λ  mv
 v= velocity of particle
• Combining these relationships: E n 2h2
8mL2

7.3 Electrons have properties of both particles and waves 28

de Broglie Explains Quantized Energy
• Electron energy is
quantized - it depends
on the integer n
• Energy level spacing
(and spectra) changes
when electron
confinement changes
• Lowest energy allowed
is for n=1 (the energy
cannot be zero, hence
atom cannot collapse)
7.3 Electrons have properties of both particles and waves 29
Wave Functions
• Wave that corresponds to the electron is called a
wave function
• Wave functions for an electron are called orbitals
• Amplitude of the wave function at a given point
can be related to the probability of finding the
electron there
• According to quantum mechanics there are
regions of the wire where the electrons will not be
found, called nodes

7.3 Electrons have properties of both particles and waves 30

Quantum Numbers
Are a shorthand to describe characteristics of an
electron’s position and to predict its behavior
• n = principal quantum number. All orbitals with the
same principle quantum number are in the same shell
• l = secondary quantum number which divides the
orbitals in a shell into smaller groups called subshells
• ml = magnetic quantum number which divides the
subshells into individual orbitals

7.3 Electrons have properties of both particles and waves 31

Quantum Numbers: What Do They Mean?
• n = roughly describes a distance of the electrons
from the nucleus.
 designated by integers: 1, 2, 3, 4, 5, 6, …
• l = describes the shape of the orbitals.
 designated with numbers : 0, 1, 2, 3, 4, 5……
 or with letters: s, p, d, f, g, h
• ml =describes the spatial orientation of the orbital.
 designated by numbers specific to the particular orbital
 range from –l to +l

7.3 Electrons have properties of both particles and waves 32

How Do Quantum Numbers Relate to Each
Other?
-1 0 +1 -2 -1 0 +1 +2
0

5p 4d
5s
4p 3d
Energy

4s
3 s 3p

2p
2s
•n
•l
•ml
1s
7.3 Electrons have properties of both particles and waves 33
Electrons Behave Like Tiny Magnets
• Electrons within atoms
interact with a magnet
field in one of two
ways:
 clockwise (spin up)
 anti-clockwise (spin
down)
• This gives rise to the
spin quantum number,
ms
• allowed values: + 1/2 or
–1/2
7.4 Electron spin affects the distribution of electrons among orbitals in atoms 34
 Pauli Exclusion Principle
• No two electrons in the same
atom can have identical
values for all four quantum
numbers
• electrons can occupy the
same orbital only if they
have opposite spin are
paired (called diamagnetic)
• Substances with more spin
in one direction are said to
contain unpaired electrons
(called paramagnetic)

7.4 Electron spin affects the distribution of electrons among orbitals in atoms 35
 Ground State Electron Arrangements
• Electron configurations list the subshells that
contain electrons and indicate their electron
population with a superscript
• Orbital diagrams-represent each orbital with a
circle (or box) and use arrows to indicate the spin of
each electron

7.5 The ground state electron configuration is the lowest energy distribution of electrons 36
among orbitals
Your Turn!

Which is not a possible set of quantum numbers

for an electron?

n l ml ms
A) 3 3 3 +1/2
B) 3 2 2 -1/2
C) 3 1 1 +1/2
D) 3 0 0 -1/2

7.5 The ground state electron configuration is the lowest energy distribution of electrons 37
among orbitals
Hund’s Rule
• Electrons fill a sublevel by occupying each orbital
individually, then by pairing if needed
• This reduces the electrical repulsion between
electrons

not

7.5 The ground state electron configuration is the lowest energy distribution of electrons 38
among orbitals
Electron Occupancy And The Periodic Table
The periodic table is divided into regions of 2, 6, 10,
and 14 columns corresponding to the maximum number
of electrons in s, p, d, and f sublevels

7.6 Electron configurations explain the structure of the periodic table 39

Sublevels and the periodic table.
• Each row (period) represents an energy level
• Each region of the chart represents a different
type of sublevel

7.6 Electron configurations explain the structure of the periodic table 40

 Where Are The Electrons?
• Each box represents room for an electron.
• Read from left to right

7.6 Electron configurations explain the structure of the periodic table 41

 Read The Periodic Table To Determine e-
Configuration
• Read from left to right
• The first e- go into the first
Energy level (period 1)
• The first type of sublevel
to fill is the “1s”
• He has 2 e-. The e-
configuration for He is: 1s2

7.6 Electron configurations explain the structure of the periodic table 42

 Learning Check
• B has 5 e- that fill the
first shell…
• …next the second shell
• There are 2 subshells in
the 2nd shell: they fill in
order of increasing
energy
• 1s22s22p1

7.6 Electron configurations explain the structure of the periodic table 43

Noble Gas Core Notation For Mn
5 2
[Ar] 4s 3d
• Find the last
noble gas
that is filled
before Mn
• Next fill the
sublevels
that follow.

7.6 Electron configurations explain the structure of the periodic table 44

Your Turn!

Which is the ground state electron configuration

of F?
A. 1s2 2s2 2p3
B. 1s2 2s2 2p2 3s2
C. 1s2 2s2 2p5
D. None of these

7.6 Electron configurations explain the structure of the periodic table 45

Your Turn!

Which of the following elements has the ground

state noble gas core configuration of [Ne]2s2?
A. Ne
B. Na
C. F
D. Mg
E. none of these

7.6 Electron configurations explain the structure of the periodic table 46

 Creating An Orbital Diagram
• Examine the electron configuration for the atom.
• For each sublevel, determine the correct number of
orbitals
 there is one box for each value of ml (2l+1 boxes)
• Note the number of electrons in each sublevel
• Distribute the electrons into the orbital, first
individually, then pairing (Hund’s rule)
 Each arrow represents an e-
• Make sure that the paired electrons have opposite spin
directions (Pauli exclusion principle)

7.6 Electron configurations explain the structure of the periodic table 47

 Orbital Diagram & e-configurations - N

5p
5s 4p
4s 3d
EPOT
3p
3s

2p
2s
Each arrow represents an electron

1s 1s2 2s2 2p3

7.6 Electron configurations explain the structure of the periodic table 48
 Orbital Diagram & e-
configurations - V

4s 3d
EPOT
3p
3s

2p
2s
Each arrow represents an electron

1s 1s2 2s2 2p6 3s2 3p6 4s2 3d3

7.6 Electron configurations explain the structure of the periodic table 49
 Learning Check:
Write electron configurations and orbital diagrams
for Na

5p
5s 4p
4s 3d
EPOT
3p
3s

2p
2s

1s Na 1s2 2s2 2p6 3s1

7.6 Electron configurations explain the structure of the periodic table 50
 Learning Check:
Write electron configurations and orbital
diagrams for As

5p
5s 4p
4s 3d
EPOT
3p
3s

2p
2s

1s As 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3

7.6 Electron configurations explain the structure of the periodic table 51
Your Turn!
Using the following notation, which is correct for the orbital
diagram for Se?
X = paired electrons _ = empty orbital \ = unpaired electron
in an orbital
A. 1s X 2s X 3s X 3d X X X X X 4s X 4p X X _
B. 1s X 2s X 3s X 4s 3d X X X X X 4p X X _
C. 1s X 2s X 3s X 4s 3d X X X X X 4p \ \ \
D. 1s X 2s X 3s X 4s 3d X X X X X 4p X \ \
E. None of these

7.6 Electron configurations explain the structure of the periodic table 52

Electronic Classification
• Core e-: complete the previously filled noble gas
• Valence e-: are in the highest energy level outside
the noble gas core. Involved in bonding.
• Pseudo-valence e- : are outside the noble gas core
in lower energy levels
 contribute to shielding
 occasionally take part in bonding

7.6 Electron configurations explain the structure of the periodic table 53

 Representative Elements
• For the representative elements (A groups):
 the electrons with the highest n value or valence shell are
normally the only electrons important for chemical
properties
 the valence electrons consist of electrons in just the s and
p subshells
• A valence configuration shows only valence
electrons
 for bromine:
Br 4s24p5

7.6 Electron configurations explain the structure of the periodic table 54

 Your Turn!
How many valence electrons are found in Fe,
[Ar] 4s2 3d6?
A. 2
B. 6
C. 8
D. None of these

7.6 Electron configurations explain the structure of the periodic table 55

Exceptions to the electronic configurations
Following the rules for Cr, Cu, Ag, and Au using
noble gas notation we expect the following:

Element Expected Experimental

Cr [Ar] 3d4 4s2 [Ar] 3d5 4s1
Cu [Ar] 3d9 4s2 [Ar] 3d10 4s1
Ag [Kr] 4d9 5s2 [Kr] 4d10 5s1
Au [Xe] 5d9 6s2 [Xe] 5d10 6s1

7.6 Electron configurations explain the structure of the periodic table 56

Uncertainty Principle:
• Erwin Schrödinger: wave is most significant
character of electrons
• Werner Heisenberg: We cannot know exactly both
the position and speed of an electron. All acts of
measurement interact with electrons.

h
xmv 
4
7.7 Quantum theory predicts the shapes of atomic orbitals 57
Orbitals Represent Uncertain Positions

• Plot shows that

electron density
varies from place
to place
• Electron density
variations define
the shape, size,
and orientation of
orbitals

7.7 Quantum theory predicts the shapes of atomic orbitals 58

“s” Orbitals And Nodes
• Orbitals get larger as the principle quantum number n
increases
• Nodes, or regions of zero electron density, appear
beginning with the 2s orbital

7.7 Quantum theory predicts the shapes of atomic orbitals 59

“p” Orbitals
• Possess a nodal plane that separates the “lobes” of
high probability
• Dot-density diagrams of the cross section of the
probability distribution of a single (a) 2p and (b)
3p orbital showing the nodal plane and the size
difference

7.7 Quantum theory predicts the shapes of atomic orbitals 60

There Are Three Different Orbitals In Each
p Subshell
• The directions of maximum electron density lie
along lines that are mutually perpendicular.
• Orbitals are labeled as px, py, and pz

7.7 Quantum theory predicts the shapes of atomic orbitals 61

 “d” Orbital Shape and Orientations

• Shape and orientation of d orbitals are more

complicated than for p orbitals.
• “f” orbitals are even more complex than the d orbitals

7.7 Quantum theory predicts the shapes of atomic orbitals 62

 Shielding And Effective Nuclear Charge
• Shielding: occurs when core electrons
block the valence electrons from
experiencing the full attraction of the
nucleus
• Effective nuclear charge (Z*eff): the
amount of positive charge “felt” by
outer electrons in atoms other than
hydrogen
 Z*eff=Z-shielding electrons
 is lower than the atomic number
because of shielding

7.8 Atomic properties correlate with an atom’s electron configuration 63

 Learning Check:

• Compare Na and K. Which has greater shielding?

K
• Compare N and O, Which has greater shielding?
neither
• Compare Na, Ca, K and O. Arrange in order of
increasing Z*eff
O>Ca>K≈Na

7.8 Atomic properties correlate with an atom’s electron configuration 64

Trends In Atomic and Ionic Radii (pm)

7.8 Atomic properties correlate with an atom’s electron configuration 65

Your Turn!

Which of the following correctly compares the sizes

of the entities?
A. Mg > Mg2+
B. O> O2-
C. Ne >Mg
D. None of these

7.8 Atomic properties correlate with an atom’s electron configuration 66

Ion vs. Atom Radii
• Positive ions are always smaller
than the atoms from which they
are formed
 due to decreased shielding effects
• Negative ions always larger than
the atoms from which they are
formed
 due to increased electron repulsion

7.8 Atomic properties correlate with an atom’s electron configuration 67

Ionization energy (IE)
• IE is the energy required to remove an electron from
an isolated, gaseous atom
X ( g )  X  ( g )  e
• Successive ionizations are possible until no electrons
remain
• Trends in IE are the opposite of the trends in atomic
size

7.8 Atomic properties correlate with an atom’s electron configuration 68

Trends in IE

7.8 Atomic properties correlate with an atom’s electron configuration 69

Successive IE

7.8 Atomic properties correlate with an atom’s electron configuration 70

Irregularities in I.E.

7.8 Atomic properties correlate with an atom’s electron configuration 71

Electron Affinity (EA)
• Is the potential energy change associated with the
addition of an electron to a gaseous atom or ion in
its ground state
 
X (g)  e  X (g)
• Addition of one electron to a neutral atom is
exothermic for nearly all atoms
• Addition of subsequent electrons always requires
energy

7.8 Atomic properties correlate with an atom’s electron configuration 72

Successive EA
Consider the addition of electrons to oxygen:

Change EA(kJ/mol)
O(g)  e  O ( g ) - -
- 141
O (g)  e  O ( g )
- - 2-
 844
Net : O(g)  2e  O ( g )  703 - 2-

7.8 Atomic properties correlate with an atom’s electron configuration 73

Trends in Electron Affinity
In general, electron affinity:
• increases (as an exothermic value) from left to right in a
period
• increases (as an exothermic value) bottom to top in a
group

7.8 Atomic properties correlate with an atom’s electron configuration 74

Learning Check

Arrange Na, Ca, N, O in order of increasing:

• ionization energy
Na> Ca> O> N
• electron affinity (as an exothermic value)
Na> Ca> O> N
• Atomic radius

Na<Ca< O< N

7.8 Atomic properties correlate with an atom’s electron configuration 75