Ch.

6-7
Quantum Mechanical
Model

Correcting/Updating the
Bohr Model of the Atom
 Quantum Mechanical Model
• Werner Heisenberg (1901-1976) German physicist
• A founder of QUANTUM MECHANICS, he is
famous for his uncertainty principle.
– To detect an electron a photon is used.
– The photon interacts with the electron and changes its
course (both position and velocity).
– There is uncertainty in trying to locate an electron (or any
other particle).
• The effect of this principle is to convert the laws of
physics into statements about relative, instead of
absolute, certainties.
 Quantum Mechanical Model
• Erwin Schrodinger used mathematical analysis to
describe position of e- around the nucleus.
• Solutions to the eqns are wave functions.
• Predict the probability of finding an e- in a
given region around the nucleus of any atom
(gave rise to Schrodinger’s Eqn…not something
you’ll ever actually use!)
The Hydrogen Atom Hotel
• Here’s the story…
 Hotel Rules = Principles of e-
Placement in Atom
• Beds closest to the game room filled first = Aufbau
Principle
– The ground state configuration for an atom results when
e- “build up” …Lower en orbitals are filled first
• Two e- per bed and must sleep head to toe = Pauli
Exclusion Principle
– An orbital (i.e. bed) can hold up to 2 e- w/ opposite spins
(more to come later…)
• E- don’t want to share a bed = Hund’s Rule
– If two or more energetically equivalent orbitals are
available (i.e. different beds in same room) then e- should
be spread out before they are paired up (aka: maximize #
unpaired e-)
Skip movie
 Probability Regions
• Because of the Heisenberg Uncertainty Principle, it is
impossible to know exactly what an electron is doing in
an atom. We can know its energy and its probable
location (where it’s likely to be 90% of the time). We call
this region of space an orbital.
• Electron density clouds (aka: probability Sample orbitals:
regions) = solutions to Schrodinger
equations
• E- has the probability of being in a certain
region of space around the nucleus = orbital
• Orbitals have different shapes and
orientation in space
• Orbitals of same type (aka: shape) are
grouped into a sublevel
• Each energy level composed of 1 or more
different sublevels
Sublevels are divided into orbitals (# of
ways of arranging sublevel on x, y, z axes
in space) = also equal to number of beds in
room
s Sublevel = 1 Orbital
 More about the s orbital
Two representations of the
Hydrogen 1s, 2s and 3s
orbitals:
(a) the electron probability
distribution
(b) the surface contains 90%
of the total electron
probability (the “size” of
the orbital by definition)
p sublevel = 3 Orbitals
d sublevel
=
5 Orbitals
f Sublevel = 7 Orbitals
 Putting it all together…
• Each energy level can hold only so many
sublevels and orbitals
• n = energy level
• As n increases, so does the number of the
sublevels (holds more electrons).
• The energy of the level increases as n
increases.
The big
picture…
 Sublevels vs. Orbitals
• Each sublevel can be arranged in different ways in
space = orbital
• Remember…each orbital is like each bed in the hotel
room!
• s = 1 #orbital
orbitals? 2 electrons
# e- max?max

• p = 3 orbitals 6 electrons
# e- max?max

• d = 5 orbitals 10 electrons
# e- max? max

• f = 7 orbitals 14 electrons
# e- max? max

• Each orbital can hold 2 electrons (just like each

bed!)
• Max #e- per sublevel = # orbitals x 2 e-
What’s in each energy level?

• n=1  s
• n=2  s, p In which energy level
• n=3  s, p, d will a “g” sublevel (the
next in line) first be
• n=4  s, p, d, f found?
• n=5  s, p, d, f
• n=6  s, p, d
• n=7  s, p
 How does this relate
to the Bohr model?
If the H electron were
to jump to n = 2, is
there any difference
in energy if it goes to
2s or 2p?
e-

What is different for other

e- e- atoms?

Check this out And this…

Aufbau: Why does 2s fill before 2p?

A Comparison of the
Radial Probability
Distributions of the 2s
and 2p Orbitals
2s orbital has greater penetration to
the nucleus. This brings the
negatively charged e- in 2s orbital
closer to positively charged nucleus
which is more stable, thus, lower in
energy.
Aufbau: 3s, 3p, 3d?
(a)Radial Probability
Distributions of the 3s
Orbital
(b)Radial probability
distribution for 3s, 3p
and 3d Orbitals

Compare penetration of 3s,

3p and 3d. How does this
related to order of filling for
these orbitals?
 Penetration Effect?
• An electron in an s orbital has a finite, albeit very
small, probability of being located quite close to
the nucleus.
• An electron in a p or d orbital on the other hand
has a node (i.e., a region where there cannot be
any electron density) at the nucleus.
• Comparing orbitals within the same shell (i.e. 3s
vs. 3p vs. 3d), we say that the s orbital is more
penetrating than the p or d orbitals, meaning
that an electron in an s orbital has a greater
chance of being located close to the nucleus
than an electron in a p or d orbital.
 The REAL Atom Hotel

Notice the splitting

of energy levels?
Notice that
orbitals of same
sublevel/energy
Remember:

Principle

level are
Aufbau

degenerate?
Note that the DE between
energy levels and sublevels for
each atom varies. Not regular
like Bohr predicted.

Note that the application of

Aufbau principle (fill orbitals
lowest in energy to highest)
results in same predicted order
for each element even if their
energies vary between
elements.

Note that the 2p orbitals are

always degenerate.

Why do the orbitals get

progressively lower in energy
as you go from Li to F? What
varies about each atom as you
go from Li to F?
 The Actual Order of Filling
1s22s22p63s2 3p64s2 3d104p65s24d105p66s24f145d106p67s25f146d107p6

Remember Aufbau Principle: lowest

energy orbitals fill first! Learn how to
follow the Periodic Table
How does the Periodic Table fit
into all this?
• The PT is arranged in the order of the e-
filling
• There are s, p, d and f regions of the PT
• Row Number or Period Number
indicates the energy level that the e- are
filling into
• Group # indicates which sublevel the e-
is filling into
 Here’s what it looks like:
I and II:#fill
up to s sublevel
n = Period

Groups III-VIII:
nfill
= period
up to p
#
Group

Transition metals sublevel

n = period # - 1fill
up to d sublevel

Lanthanids/Actanides fill up to f
n =sublevel
period # - 2
 Predicting Electron Configuration and
Orbital Diagrams

• H
• He
• Li
• Be
• B
• C
• N
1s 2s 2p Back to PT
Predicting Electron Configuration and
Orbital Diagrams

1
• H 1s1 # Valence e-?
2
• He 1s2 1
• Li 1s22s1 2
3
• Be 1s22s2

• B 1s22s22p1

• C 1s22s22p2 4

• N 1s 2s 2p
1s22s22p3 5
Let’s see more!
 Practice
• Write the complete electron
configuration for each element:
Al (Z = 13)

Ca (Z = 20)

Br (Z = 35)
 Answers
• Write the complete electron
configuration for each element:
Al (Z = 13)
1s22s2 2p63s2 3p1
Ca (Z = 20)
1s22s2 2p63s2 3p64s2
Br (Z = 35)
1s2 2s2 2p63s2 3p64s2 3d104p5
Click for more practice
 But it’s too much to write!
• Write the electron configuration for Radium.
• The shorthand (or Noble Gas Notation) is a
shorter way to express the configuration of
the element.
• Write the symbol for the noble gas
immediately preceding your element in
brackets. Ex. [Rn]
• Then, complete the configuration by picking
up where the noble gas left off. Ex. [Rn] 7s2
 Practice
• Write the shorthand e- configuration for
each element:
Al (Z = 13)

Also indicate the

Ca (Z = 20) number of valence
e- the atom has.

Br (Z = 35)
 Answers
• Write the shorthand electron
configuration for each element:
Al (Z = 13)
[Ne] 3s2 3p1 3 valence e-

Ca (Z = 20)
2 valence e-
[Ar] 4s2
Br (Z = 35)
[Ar] 4s2 3d104p5 7 valence e-
Click on this link and then select
Electron Configuration
 Quick Review
• Elements are represented by the
electron configurations below. To what
group would each element belong?
[Ne] 3s23p1

[Ar] 4s23d104p5

1s22s22p63s23p64s23d104p65s2 4d105p66s1
[Kr] 5s24d105p6
 More Practice:
• Write the complete e-configuration for:
Cs (Z=55)

Also indicate the

Pb (Z=82) number of unpaired e-
the atom has.

U (Z=92)
 More practice:
• Write the complete e-configuration for:
Cs (Z=55) 1 unpaired e-
1s22s22p63s2 3p64s2 3d104p65s24d105p66s1

2 unpaired e-
Pb (Z=82)
1s22s22p63s2 3p64s2 3d104p65s24d105p66s24f145d106p2

U (Z=92) 4 unpaired e-

1s22s22p63s2 3p64s2 3d104p65s24d105p66s24f145d106p67s26d15f3

 The exceptions:
• Some elements don’t fill exactly as the PT
predicts.
Cr (Z=24)

Cu (Z=29)

Pr (Z=59)
 The exceptions:
Notice the half-filled s and d orbitals? Aufbau principle
Cr (Z=24) suggests this is the lowest energy ground state
configuration. Likely due to the degenerate 4s and 3d
[Ar] 4s13d5 orbitals in this atom.

Cu (Z=29) Notice the half-filled s and filled d orbitals? Why?

Aufbau principle suggests that this is the lowest
[Ar] 4s13d10 energy ground state configuration. Likely due to the
degenerate 4s and 3d orbitals in this atom.

Pr (Z=59) Notice the missing d electron? Why? Aufbau principle

suggests that this is the lowest energy ground state
[Xe]6s24f3 configuration. Some lanthanides and actinides do this.
Be aware but don’t memorize.
 What about ions?
• Use the PT to determine the Noble Gas
notation for:
Cs+1

Pb+4

Se2-
 Answer:
• Anions put e- into a valence shell to fill it
• Cations lose e- from valence shell
Cs+1
[Kr] 5s24d105p6 (removes the outer 6s1 e-)
Pb+4
[Xe] 4f145d10 (lost e- from 6s and 6p)
Se2-
[Ar] 4s23d104p6 (adds to the 4th en level)
Evidence for Electron Configurations
• Photoelectric Spectroscopy (PES)
– The PES experiment begins with absorption of high
energy photons that carry more energy than the
ionization energy of the atom
– The XS energy is carried off by the e- ejected from
the atom in the form of KE
– PES allows us to measure the en needed to remove
any e- on an atom (Ionization Energy)
– Data from PES expt are obtained as peaks in a
spectrum that plots intensity of observed signal (# e-)
vs. en needed to eject an e- (IE)
– If height of one peak is in 2:1 ratio w/another, then
twice as many e- were in that energy level.
– http://bit.ly/1195Ahl for more information
 Evidence for Electron
Configurations
• http://www.chem.arizona.edu/chemt/Flash/
photoelectron.html
 Sample Spectrum Why is there
such a large
difference in
energy between
the peaks at
0.74, 5.31 and
9.07 eV, and the
peak at 126 eV?

Which peak in the spectrum represents What is the relevance of the

electrons that are closest to the nucleus? relative height of the peaks at
HDYK? 5.31 eV and 9.07 eV?
 If you did not know it was Mg
1. Assuming that the PES data shows ALL
of the electrons present in the atom,
identify the element. Write the electron
configuration.
2. Still applying the assumption in #1, which
specific electrons are associated with the
peak at 126 eV?
3. What does a relatively low value of
energy tell you about the relative position
of the electrons within any atom?
Example:

Given PES Data above, answer the following questions:

1. Assuming all electrons are represented above, identify the element
and write the complete electron configuration.
2. Which electrons in the configuration from #1 represent those
associated with peaks at 0.63 and 0.77 eV? Why? HDYK?
Where would you expect the peaks for the valence e- of O relative to that of N?

Does the energy of these e- surprise you?

 True or False?
• The photoelectron spectrum of Mg2+ is expected
to be identical to the photoelectron spectrum of
Ne.
– FALSE: Since these 2 species are isoelectronic,
same number of electrons, it would initially lead one
to believe they would be the same. However, Mg has
12 protons, whereas Ne has 10, therefore there is a
different level of interaction between the nucleus and
the electrons. The photoelectron spectrum would be
different.
• The photoelectron spectrum of 35Cl is identical to
the photoelectron spectrum of 37Cl.
– TRUE: The photoelectron spectrum would be the
same since the Zeff and number of electrons is the
same.
 For more info/practice:
• http://www.mro-
chemweb.com/apchem/docs/hoans/pes.pd
f
• http://www.youtube.com/watch?v=vANbxo
zsRSA
7.6 Periodic Trends

Includes information from

8.7 Electronegativity
 Periodic Trends
• Now that you’ve seen how the PT is arranged (in
families, periods, by atomic number) you can also
look for trends that arise within families or across
a period
• The following properties have variance across the
periodic table and repeat themselves in
subsequent periods periodically…hence the name
“Periodic Table”
– atomic radius
– ionic radius
– ionization energy
– electron affinity
– electronegativity
Periodic Trends Music Video
Nuclear Charge and Electron Shielding
(13 min 37 sec)
http://wps.prenhall.com/wps/media/objects/4677/4790120/ch05_11.htm
http://wps.prenhall.com/wps/media/objects/4677/4790120/ch05_15.htm
Periodic Trends – Overview (9min 3 sec)
 What causes these trends?
• Remember Nuclear Charge (Z) = total positive
charge of nucleus = Increases L to R in period
• Do all electrons “feel” the same nuclear charge?
• Turns out that core electrons shield, or screen
the outer electrons from the nucleus b/c of
repelling forces between electrons.
• The positive charge that an electron actually
experiences from the nucleus is called the
effective nuclear charge, Zeff (usually
somewhat less than the actual nuclear charge)
• Indirect relationship between # of shielding
electrons and Zeff.
Compare shielding experienced by valence e- of:
(1) Mg and Ca (2) C and F
E- of interest does not feel the same attraction of protons b/c inner/core e- have
shielded the nucleus (reducing Z to Zeff). The greater the shielding, the “easier” it is
to lose an electron (lower energy requirement to remove e-).
 Atomic Radius (AR)
• Definition: One half the distance
between nuclei of atoms of the same
element, when the atoms are bound by
a single covalent bond or are in a
metallic crystal.
 Atomic Radius (AR)
• Trend:
– Down Group = increase
– L to R in Period = decrease
• Explain Trend:
– Down Group = inc # shielding e- as add new en
levels = dec Zeff = dec attractions to valence e-
– L to R in Period = inc Z as add more p+ which
increases attraction to outer e-
• Deviations: none for you to know at this
time
Ionic Radius (IR)
 Ionic Radius (IR)
• Trend:
– Down Group = increase
– L to R in Period = decrease
• Explain Trend:
– Down Group = same as AR
– L to R in Period = same as AR
• Deviations: none

Watch this animation for more information.

 Ionization Energy (IE)
• Definition: Energy change associated with
the loss of 1 valence electron from 1 mole of
gaseous element. (positive value,
endothermic change)
X (g) + IE  X+1 (g) + e-
What this means:
larger IE = more en absorbed to remove e- =
reflects greater attraction to e-
 Ionization Energy (IE)
• Trend:
– Down Group = decrease
– L to R in Period = increase
• Explain Trend:
– Down Group: inc shielding e- = dec Zeff = dec
attraction to outermost
Downe- = easier to remove
group?
outermost e- = lower IE
– L to R in Period = inc Z = inc attraction to
outermost e- = harder Ltoto R?
remove outermost e- =
higher IE
 Ionization Energy (IE)
• Deviations:
Group 2 – 3: Grp 2 has greater IE than 3 (which is opposite the trend)
b/c the s electrons penetrate more closely to the nucleus and are slightly
more stable (require greater input of energy to dislodge). Grp 3 has one
e- in the p which is “easier” to remove (requires lower input of energy)
b/c the p e- does not penetrate to the nucleus as well as the s electrons.
The p electron is slightly less stable than the s electrons so less energy
must be provided to cause that single p electron to overcome the nuclear
attraction. This explains the drop in IE as you go from grp 2 to 3.

Group 5 – 6: Grp 5 has higher IE than 6 (which is opposite the trend).

Grp 5 has 3 electrons in the p sublevel (each unpaired) while Grp 6 has
4 electrons (2 of which are paired). Grp 6 should experience greater Z
and, therefore, greater nuclear-electron attraction. However, the paired
e- in one of the p orbitals of Grp 6 elements experience greater electron-
electron repulsion which means one of those electrons will be more
easily lost than any of the electrons from the half-filled p sublevel of Grp
5. This explains the drop in IE as you go from grp 5 to 6.
 Electron Affinity (EA)
• Definition: Energy change associated with the
gain of 1 valence electron by 1 mole of gaseous
element (often negative value, exothermic
change)
Y (g) + e-  Y-1 (g) + EA
• What this means:
– a large negative EA = more en released b/c of greater
attractive forces felt by the new e- = e- placed in more
“stable” position outside the nucleus (i.e. closer to
nucleus, less shielding)
– If EA is positive, this means atom must be “paid” to
take an e- (which means the atom must put the e- in a
high energy position, further from nucleus or with
greater shielding, resulting in less attraction to
nucleus)
 Electron Affinity (EA)
• Trend: (not as “smooth” as other trends)
– Down Group = decrease (releases less energy)
– L to R in Period = increase (releases more
energy)
• Explain Trend:
– Down Group = inc shielding e- = dec Zeff = less
attraction for own outer e- = less attraction for
Down group?
“free” e- = gives up less en when e- added
– L to R in Period = inc Z = greater attraction for
own outer e- = greater L toattraction
R? for “free” e- =
gives up more en when e- added
 Electron Affinity (EA)
• Deviations:
Group 5: EA values tend to drop. These elements
have a half-filled p sublevel (3 unpaired e-) and, due
to greater stability conferred by this scenario, do not
release much (or any) en to gain an extra p e- that
will pair up w/an existing one (puts two neg charged
particles in closer proximity which increases electron
repulsion).
Group 8: Tend to have EA values of zero or some may
be positive. They have full outer en level which
confers greatest stability. To gain an e- would cause
the start of a new energy level and require more
energy. They either won’t give any en to gain e- or
must be “paid” to take extra e-.
 Electronegativity (EN)
• Definition: a value that represents the
relative ability of an atom to attract e-
towards itself in a bond
– EN is NOT an energy
– Scale ranges from 0 - 4
• What this means:
larger EN = atom has greater attraction for
e- in a bond
 Electronegativity (EN)
• Trend:
– Down Group = decrease
– L to R in Period = increase
• Explain Trend:
– Down Group = inc shielding e- = dec Zeff =
decrease pull on own valence e- = decrease pull
on any e- in bond
– L to R in Period = inc Z = increase pull on own
valence e- = increase pull on any e- in bond
 Electronegativity (EN)
• Deviations:
Group 8: Most Grp 8 elements tend to have
EN = 0 b/c they have full outer en levels
(most stable configuration). This means
they tend not to form bonds like other
elements. Some Grp 8 elements do have
EN values, though, b/c they are large
enough to form bonds (energetically
favorable to share e- that are quite far from
nucleus).
 Metallic Character and Reactivity
• MC = every element has some metallic
character
– Those elements that lose e- more easily than
others are considered more metallic
• MR = refer to the relative ability of M to lose
e- (which is what they do during chem rxns)
– Watch this video
• Nonmetallic character and reactivity are the
exact opposite
Metallic Character and Reactivity
Consecutive Ionization Energies
• 1st IE = energy reqd to remove 1st outermost e-
• 2nd IE = energy reqd to remove 2nd outermost
e-, etc.
• Each consecutive IE increases b/c there is a
greater ratio of p+ to e- (increasing the
attraction on existing e-)
• Can use the consecutive IE’s to determine
which family an element belongs to
Consecutive Ionization Energies
First, Second, Third, and Fourth Ionization Energies
of Sodium, Magnesium, and Aluminum (kJ/mol)

Notice the large jump from 1st IE to 2nd IE for Na or

from 2nd IE to 3rd IE for Mg or from 3rd IE to 4th IE for Al.
What does this mean? Write e- config for each.
 Consecutive Ionization Energies
Predict the group in the periodic table in which an element with
the following ionization energies would most likely be found.
1st IE = 786 kJ/mol
2nd IE = 1577
3rd IE = 3232
4th IE = 4355
5th IE = 16,091
6th IE = 19,784

Ans: This is likely a GRP IV element. The large jump from 4th
IE to 5th IE means that it has 4 valence e- and removing a 5th
e- will remove a “core” e- (from a full sublevel).
Ground vs. Excited State Configuration

• Which configurations correspond to an

excited state for an atom?
– 1s22s22p63s13p1
– 1s22s22p63s23p64s23d104p2
– [Rn] 7s25f76d1
– [Kr]5s24d105p56s1