Chapter 6

Electronic Structure
of Atoms
 How do We get From
Here….. To here

Dalton, indivisible Schroedinger/Heisenberg

Quantum mechanical object
 Theories to
explain them More
Experiments
experiments
Atomic spectra Quantum theory Atomic structure
• Bunsen, Kirchhoff, • Plank,1900 • Dalton, 1803
1860 Ø Black body Ø atomic nature
Ø 1st spectroscope radiation
• Faraday, 1834
Ø 1st line spectrum • Einstein, 1905 Ø Electricity & Mag.
• Lockyer, 1868 Ø Photoelectric
effect • Thompson, 1807
Ø He in solar system Ø electrons e/m
• Balmer,1885 • Millikan, 1911
Ø H line spectrum Ø oil drop
• Rutherford, 1911
• Bohr, 1913 Ø gold foil/nucleus
Ø Applied to atom
structure
Electro-magnetic radiation (light)
• The nature of light
Ølight is a wave
• The nature of waves
ØWhat is a wave?
ØWhat is waving?
 Waves
A

time

• Wave: some sort of periodic function

Ø something that periodicaly changes vs. time.
• wavelength (λ): distance between equivalent points
• Amplitude: “height” of wave, maximum
displacement of periodic function.
 Waves
• The number of waves
Higher frequency passing a given point per
shorter wavelength unit of time is the
frequency (ν).
• For waves traveling at
the same velocity, the
longer the wavelength,
the smaller the
lower frequency frequency.
longer wavelength
 Waves

v = wavelength x frequency
meters x (1/sec) = m/sec

v = λν
 Waves
Major question:
• What is waving?
• water wave:
Ø water height(pressure)
• Sound wave:
Ø air pressure
• Light?
 Light waves.

• What is waving? Electric field, and

perpendicular magnetic field.
• Faraday thought this, Maxwell proved it.
 Electromagnetic Radiation

• All electromagnetic radiation travels the speed of

light (c), 3.00 × 108 m/s (in a vacuum).
• Therefore: c = λν
 Electromagnetic Radiation

• All electromagnetic radiation travels the speed of

light (c), 3.00 × 108 m/s (in a vacuum).
• Therefore: c = λν
 Speed of light in other materials
Index of refraction is:
The speed of light is only a constant in a vacuum.

n = c/v
The index of refraction of some common materials are given
below.
material n material n
Vacuum 1 Crown Glass 1.52
Air 1.0003 Salt 1.54
Water 1.33 Asphalt 1.635
Ethyl Alcohol 1.36 Heavy Flint Glass 1.65
Fused Quartz 1.4585 Diamond 2.42
Whale Oil 1.460 Lead 2.6
Values of n come from the CRC Handbook of Chemistry and
Physics
The major issue of late 19th century
physics
• What is light?
• What is the relationship between light
and energy?
• How does light interact with matter?
The three mysteries of 19th century physics
Mystery #1: Blackbody radiation

• Why does metal glow

when heated?
• K.E. of electrons
• What light is given
off?
Black Body Radiation

Spectral output of a black body.

Black shows that predicted from
classical electricity & magnetism
Colored curves are what you
actually get.
Light is emitted when atoms
vibrate (or oscillate), but they
can only oscillate with an energy
given by:
• E = nhν
Mystery 1: Black body radiation
• Higher T leads to shorter
wavelength of light
• More K.E., more E
• Must be relationship
between E and wavelength
• Plank concluded that
energy is quantized. It
comes in packets (like fruit
snacks) and is proportional
to frequency:
E = hν
where h is Planck’s
constant, 6.63 × 10−34 J-s.
The minimum packet of E.
What did Einstein get the Nobel
Prize for?
Mystery #2: The Photo-electric effect

Note, this is what a photo cell does

Turn light into work (current)
 What might you expect what do you see?
(from normal waves)

I I Constant ν

K. E. e- K. E. e-

K.E. K.E.
e- e-

ν ν hν

current Ihigh current Ihigh

(#e-) (#e-)
Ilow Ilow

ν ν
Einstein: Light is both a particle and a wave.
e- K.E. “escape energy”
Ephoton = 1/2mv2 + hνο = Εelectron
e-
Light comes in packets of energy.
Each packetruns into one electron.
Each packet must have enough E to break electron loose.
The rest of the energy goes into kinetic energy.

Frequency tells us the E of each packet.

I tells us how many packets/second we get.
More packets, more current (more electrons e- hν
knocked off).
metal
 The Nature of light Energy

• Energy, λ, ν, related:

c = λν
E = hν

c= speed of light in vacuum,

constant
 Mystery number 3: element line spectrum

Gas discharge tube

(full of some elemental
gas)
Gives off specific
frequencies of light
only.
Different elements give
off different colors.
i.e. different energies.

Hydrogen Neon
 The Nature of Light

White light shows a

continuous spectrum

• A line spectrum of discrete wavelengths is

observed from an element
Hydrogen Line spectra

Johann Balmer, School teacher

Just figured out that the lines fit a simple equation:

1 1 1
= (R H )( 2 − 2 )
λ n1 n 2
RH=constant
n1 and n2 are integers
But why?
 Light and
matter
• Niels Bohr adopted
Planck’s assumption and
explained these phenomena
in this way:
1. Electrons in an atom can
only occupy certain orbits
(corresponding to certain
energies).
 Light and
matter
• Niels Bohr adopted
Planck’s assumption and
explained these phenomena
in this way:
2. Electrons in permitted
orbits have specific,
“allowed” energies;
Light and matter

• Niels Bohr adopted

Planck’s assumption and
explained these
phenomena in this way:
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
Light and matter
The energy absorbed or emitted
from electron promotion or
demotion can be calculated by the
equation:
1 1
ΔE = −RH ( nf2
- n2 )
i

where RH is the Rydberg

constant, 2.18 × 10−18 J, and ni
and nf are integers, the initial and
final energy levels of the electron.
 Bohr.
• Using a model
that had
electrons
orbiting the
nuceus like
planets, Bohr
could explain
H, but no other
elements.
1
•1 Too simple.
ΔE = −RH ( nf2 - n i2 )
RE = 1/2mec2 α2
 The Wave Nature of Matter
• Louis de Broglie: if light can be a
particle, maybe matter can be wave-
like.
Velocity = λν
like E=mc
2

velocity
ν=
λ
2 velocity
E = m(velocity) = hν = h
λ
h
λ=
m(velocity)
 Wave-like nature of matter
h
λ = mv
However, the higher the mass, the smaller the
wavelength & h=6.63 × 10−34 J-s, a really small
number.

Example; What is λ for a 1 g ball?

λ = 6.63x10-34kgm2/s = 6.63 x 10-31 m
.001kg(1m/s)

wavelengths of everyday objects too small to measure.

 Wave-like nature of matter

• What about an electron? v = 6 x 106 m/s:

• m = 9.1 x 10-28 g.
λ = 6.63x10-34kgm2/s = 1.22 x 10-10 m = .122 nm
9.1 x 10-28 (6 x 106 m/s)
Wavelength of X-rays
Electron microscopy
Because electron
wavelengths are very
small, you can use
them to look at very
small things.

HIV virus
100 nm, (light
microscope limit 400
nm)

T-lymphocyte
Modified picture of the atom
 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
• our uncertainty of the whereabouts of an
electron can be greater than the size of the
atom!
This is a result of the wave/particle duality of matter
 “The clues”
• 1. Plank: E of light is quantized & depends on
frequency
• 2. Einstein/photo-electric effect: Light behaves like a
particle when it interacts with matter
• 3. Emission spectra/Bohr: Potential E. of electrons
are quantized in an atom
• 4. Debroglie: wave/particle duality of electrons
(matter).
• 5. Standing waves: are quantized inherently

Born/Schroedinger/Jordan: use standing wave

analogy to explain electron P.E. in atoms.
Quantum Mechanics
 l=(1/2)λ Standing waves
1νΟ=frequency
nodes = 2 (gotta have 2)

l = (2/2)λ = λ
2νΟ=frequency
nodes = 3 Allowed ν and λ
quantized.
l = (n/2)λ,
l=(3/2)λ n is integer/quantum
3νΟ=frequency
nodes = 4
#
frequency = nνΟ
l=(4/2)λ=2λ
4νΟ=frequency
nodes = 5

l
 Quantum mechanics
• Each electron can be explained using a
standing wave equation (wavefunction)
• Quantized frequency corresponds to
quantized Energy (Debroglie, Plank,
etc.)
• Integer values are critical to this
description: quantum numbers.
 Quantum mechanics
y Examples of wave equations
y = sinx
Propagating wave
x

Ψ 2 πx
Ψ= sin
l l Standing wave
x
l=1/2λ
νΟ=frequency
nodes = 2
l
€
 Quantum mechanics
• Using math we do NOT want to deal with, you
can do the same thing for an electron in
hydrogen:
Ψ

1 −r
Ψ= e
π r
But what, physically is Ψ? What is waving?
Born (1926): Ψ2= probability/volume of finding the electron.
 Quantum Mechanics
Plot of Ψ2 for hydrogen atom.

The closest thing we now have

to a physical picture of an
electron.

90% contour, will find electron in

blue stuff 90% of the time.
 Quantum Mechanics
• The wave equation
designated with a lower
case Greek psi (ψ).
• ψ2, gives the probability
density of electron location.
• Where it’s “most likely” to be
 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 (integers)
• Why three?
 Quantum numbers
• 3 dimensions.

• Need three quantum numbers to define

a given wavefunction.
• Another name for wavefunction:
Orbital (because of Bohr).
Principal Quantum Number, n
• The principal quantum number, n,
describes the energy level on which
the orbital resides.
• Largest E difference is between E levels
• The values of n are integers > 0.
• 1, 2, 3,...n.
Azimuthal Quantum Number, l
• defines shape of the orbital.
• Allowed values of l are integers ranging
from 0 to n − 1.
• We use letter designations to
communicate the different values of l
and, therefore, the shapes and types of
orbitals.
 Azimuthal Quantum Number, l
l = 0, 1...,n-1
Value of l 0 1 2 3
Type of orbital s p d f

So each of these letters corresponds to a shape of orbital.

Magnetic Quantum Number, ml
• Describes the three-dimensional
orientation of the orbital.
• Values are integers ranging from -l to l:
−l ≤ ml ≤ l.
• Therefore, on any given energy level, there
can be up to:
• 1 s (l=0) orbital (ml=0),
• 3 p (l=1) orbitals, (ml=-1,0,1)
• 5 d (l=2) orbitals, (ml=-2,-1,0,1,2)
• 7 f (l=3) orbitals, (ml=-3,-2,-1,0,1,2,3)
Magnetic Quantum Number, ml
• Orbitals with the same value of n form a shell.
• Different orbital types within a shell are
subshells (s, p, d, f).
s Orbitals
• Value of l = 0.
• Spherical in shape.
• Radius of sphere
increases with
increasing value of n.
s Orbitals

s orbitals: n−1
nodes.
Node: 0 amplitude
0 probability
 p Orbitals
• Value of l = 1.
• Have two lobes with a nodal plane between
them.

Note: always 3 p orbitals for a given n

 d Orbitals
• Value of l is 2.
• 2 nodal planes
• Four of the five
orbitals have 4
lobes; the other
resembles a p
orbital with a
doughnut around
the center.

Note: always 5 d orbitals for a given n.

 Orbitals and nodes
Orbital Symmetry Node geometry Spherical nodes/shell* Orbitals/set

s spherical spherical n-1 1

p cylindrical 1 planar n-1 3

around x, remainder
y, or z axis spherical

d complex 2 planar surfaces n-2 5

diagonal to
Cartesian axis;
remainder spherical

f complex complex n-3 7

* n = the shell, with n = 1 the ground state or lowest possible energy shell. Thus n may
have integral values from 1 - infinity.
 Energies of Orbitals
• For a one-electron
hydrogen atom,
orbitals on the same
energy level have
the same energy.
• That is, they are
degenerate.
Energies of Orbitals
• As the number of
electrons increases,
though, so does the
repulsion between
them.
• Therefore, in many-
electron atoms,
orbitals on the same
energy level are no
longer degenerate.
Energies of Orbitals
• For a given energy level
(n):
• Energy:
• s<p<d<f
• s lowest energy, where
electrons go first
• Next p
• Then d

Why?
The closer to the nucleus, the lower the energy
 The problem with quantum
mechanics
• It’s not hard to solve equations for the various
wavefunctions if they are all alone (like H)
• The problem is what happens in the presence of other
electrons
• The electron interaction problem
• Electron interaction so complex, exact solutions are
only possible for H!
• Why?
Ø Electron probabilities overlap a lot, must interact a lot,
repulsion keeps them from ever “touching”
 Spin Quantum Number, ms

• A fourth dimension
required. Why?
 Spin Quantum Number, ms

• A fourth dimension
required. Why?
• Time. Adding time
changes E
• Another integer
(quantum number)
needed.
• Time dependent
Schroedinger equation.
 Spin Quantum Number, ms

• This leads to a fourth

quantum number, the
spin quantum number
ms.
• The spin quantum
number has only 2
values +1/2 and -1/2
• Describes magnetic
field vector of electron
 Why do we call it “spin”

Because electrons
behave like little
magnets

Note: apparently
only two values for
the magnetic field
 Spin Quantum Number, ms

• And charges that

spin produce
magnetic fields
 Pauli Exclusion Principle

• No two electrons in the

same atom can have
exactly the same energy.
• No two electrons in the
same atom can have
identical sets of quantum
numbers.
 Electron Configurations Every
electron has a home

• Address of each electron unique

• Address consists of four numbers:
• n,l,ml,ms
• Example:
• 578 S Shaw Ln. East Lansing MI
• Note, in an address each part
depends on others
• Rome Ga, not the same as Rome
Italy.
• QM are the same.
Electron Configurations
• Distribution of all
electrons in an atom
• Consist of
Ø Number denoting the
energy level
Electron Configurations
• Distribution of all
electrons in an atom
• Consist of
Ø Number denoting the
energy level
Ø Letter denoting the type
of orbital
Electron Configurations
• Distribution of all
electrons in an atom.
• Consist of
Ø Number denoting the
energy level.
Ø Letter denoting the type
of orbital.
Ø Superscript denoting the
number of electrons in
those orbitals.
 Orbital Diagrams
• Each box represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
arrow represents the 1s22s1
spin of the electron.
 Hund’s Rule
(of maximum multiplicity)

“For degenerate orbitals,

the lowest energy is
attained when the
number of electrons with
the same spin is
NOT: maximized.”
Electron configurations
Why do we accept this wacko stuff?

• It must explain all the data

• It should predict things

• Q.M. is consistent with all our data (photoelectric

effect, emission spectra of elements, dual wave/
particle weirdness, etc.
• One prediction: elements with similar electron
configuration should have similar chemical properties
Why do we accept this wacko stuff?
It predicts the periodicity of the periodic table!!

• We fill orbitals in increasing order of energy.

• Different blocks on the periodic table, then
correspond to different types of orbitals.
Why do we accept this wacko stuff?
It predicts the periodicity of the periodic table!!
• Remember: The
periodic table was
arranged the way it
was based on
chemical properties.

• Totally empirical, until

now. Based only on
observation.
 Periodic Table

• Periodic table tells you about the last electron that

went in!!!
• Periodic table also makes it easy to do electron
configurations.
Short cut for writing electron configurations
Electron configurations of the elements
Some Anomalies
Some
irregularities
occur when there
are enough
electrons to half-
fill s and d
orbitals on a
given row.
Some Anomalies

For instance, the

electron
configuration for
Chromium, is
[Ar] 4s1 3d5
rather than the
expected
[Ar] 4s2 3d4.
Some Anomalies
• This occurs
because the 4s
and 3d orbitals
are very close in
energy.
• These anomalies
occur in f-block
atoms, as well.
 What’s on the exam?

• Chapter 3, limiting reagents

• Chapter 4, (everything)
• Chapter 5 (everything)
• Chapter 6 (everything)
 Chapter 4.
Solution stoichiometery
Strong vs. weak electrolytes
Know strong electrolytes
strong acids
soluble salts

precipitation reactions
Ionic equation
net ionic equation
Neutralization reactions
gas forming reactions
H2CO3 ---- CO2 H2O
Molarity
Dilution
Titration
 Chapter 4.
Solution stoichiometery
Molarity
Dilution
Titration
Oxidation reduction
assigning oxidation numbers
who is oxidizing and reducing?
activity series
 Chapter 5
• Heat and work
• E=q+w
• H is q at constant P
• Hess’s law problems
• Heat of formation problems
• Calorimetry problems
 Chapter 6
• History of Light
• Electromagnetic radiation order
• Blackbody radiation
• Photo electric effect
• E = hν
• Quantum numbers
What are they for?
Why are there 3 or 4?
What does each stand for?
What is their relationship (l= 0,1, 2…n-1)
Electron configurations using the periodic table
Ch. 3: Limiting reagent Test breakdown:
Ch. 4: CH 6.
Ø Neutralization
Ø str./weak electrolyte E=hv
Ø Solution stoich EM radiation
Theory
Ø Acid/base rxn calc./neut.
QM numb
Ø Ox Numbers Electron config (2)
Ø Act. Series Ch. 5
Orbital shapes
heat/work/change in E
PV work
State functions
Delta H formation
Enthalpy of rxn calc
Hess Law
Calorimetry
Enthalpy of phase change
The Nobel Prize in Chemistry 2008
Roger Kornberg
X-ray crystallography
How does RNA Pol II
decode DNA into RNA?
 Nobel Prize in Chemistry
• Green Fluorescent protein

Marty Chalfie
Osamu Shimonura
 GFP

Cerebral cortex
Roger Tsien Tsien/Chalfie
Lictman/Sanes