Waves

• To understand the electronic structure of

atoms, one must understand the nature of
electromagnetic radiation.
• The distance between corresponding points
on adjacent waves is the wavelength ().
Waves
• The number of waves
passing a given point per
unit of time is the
frequency ().
• For waves traveling at
the same velocity, the
longer the wavelength,
the smaller the
frequency.
 Electromagnetic Radiation

• All electromagnetic
radiation travels at the
same velocity: the
speed of light (c), 3.00
 108 m/s.
• Therefore,
c = 
Visible light is only one form of electromagnetic
radiation; all visible light is electromagnetic
radiation, but not all electromagnetic radiation is
visible light.
Both visible light and X rays travel at the same
speed, about 186,000 miles per second.
 SAMPLE EXERCISE 6.1 Concepts of Wavelength and Frequency

Two electromagnetic waves are represented in the image below. (a) Which
wave has the higher frequency? (b) If one wave represents visible light
and the other represents infrared radiation, which wave is which?
Solution (a) Thelower wave has a longer wavelength (greater distance between
peaks). The longer the wavelength, the lower the frequency ( = c/ ). Thus, the
lower wave has the lower frequency, and the upper one has the higher frequency.

(b) The electromagnetic spectrum (Figure 6.4) indicates that infrared

radiation has a longer wavelength than visible light. Thus, the lower wave
would be the infrared radiation.
 PRACTICE EXERCISE
If one of the waves in the image above represents
blue light and the other red light, which is which?

Answer: The expanded visible-light portion of Figure 6.4 tells you that red
light has a longer wavelength than blue light. The lower wave has the longer
wavelength (lower frequency) and would be the red light.
SAMPLE EXERCISE 6.2 Calculating Frequency from Wavelength

The yellow light given off by a sodium vapor

lamp used for public lighting has a wavelength
of 589 nm. What is the frequency of this
radiation?

Solve: Solving Equation 6.1 for frequency gives  = c/ . When we insert the
values for c and , we note that the units of length in these two quantities are
different. We can convert the wavelength from nanometers to meters, so the
units cancel:

Check: The high frequency is reasonable because of the short wavelength.

The units are proper because frequency has units of “per second,” or s–1.
PRACTICE EXERCISE
(a) A laser used in eye surgery to fuse detached
retinas produces radiation with a wavelength of
640.0 nm. Calculate the frequency of this
radiation. (b) An FM radio station broadcasts
electromagnetic radiation at a frequency of 103.4
MHz (megahertz; MHz = 106 s–1). Calculate the
wavelength of this radiation.

Answers: (a) 4.688 1014 s–1, (b) 2.901 m

The Nature of Energy
• The wave nature of light
does not explain how
an object can glow
when its temperature
increases.
• Max Planck explained it
by assuming that
energy comes in
packets called quanta.
As temperature increases, the average energy of the
emitted radiation increases. Blue-white light is at
the shorter wavelength (higher energy) end of the
visible spectrum while red light is at the longer
wavelength (lower energy) end of the visible
spectrum.
 The Nature of Energy
• Einstein used this
assumption to explain the
photoelectric effect.
• He concluded that energy
is proportional to
frequency:
E = h
where h is Planck’s
constant, 6.63  10−34 J-s.
 The Nature of Energy
• Therefore, if one knows the
wavelength of light, one
can calculate the energy in
one photon, or packet, of
that light:

c = 
E = h
 SAMPLE EXERCISE 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light
whose wavelength is 589 nm.
Plan: We can use Equation 6.1 to convert the wavelength to frequency:
We can then use Equation 6.3 to calculate energy:

Solve: The frequency, , is calculated from the given wavelength.

The value of Planck’s constant, h, is given both in the text and in the table of physical
constants on the inside front cover of the text, and so we can easily calculate E:

Comment: If one photon of radiant energy supplies 3.37  10–19J, then one mole of
these photons will supply

This is the magnitude of enthalpies of reactions (Section 5.4), so radiation can break
chemical bonds, producing what are called photochemical reactions.
 SAMPLE EXERCISE 6.3 continued

PRACTICE EXERCISE
(a) A laser emits light with a frequency of 4.69  1014 s–1.
What is the energy of one photon of the radiation from this
laser? (b) If the laser emits a pulse of energy containing
5.0  1017 photons of this radiation, what is the total energy
of that pulse? (c) If the laser emits 1.3  10–2 J of energy
during a pulse, how many photons are emitted during the
pulse?

Answers: (a) 3.11  10–19 J, (b) 0.16 J, (c) 4.2  1016 photons
Electrons would be ejected, and they would have
greater kinetic energy than those ejected by yellow
light.
The Nature of Energy
Another mystery
involved the
emission spectra
observed from
energy emitted by
atoms and
molecules.
 The Nature of Energy
• One does not observe
a continuous
spectrum, as one gets
from a white light
source.
• Only a line spectrum of
discrete wavelengths
is observed.
Photons of only certain allowed frequencies can be absorbed
or emitted as the electron changes energy state.
The Nature of Energy
• 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).
The Nature of Energy
• Niels Bohr adopted Planck’s
assumption and explained
these phenomena in this
way:
2. Electrons in permitted orbits
have specific, “allowed”
energies; these energies will
not be radiated from the atom.
The Nature of Energy
• 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 = h
The Nature of Energy
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation:
1 1
E = −RH ( nf2
- 2
ni )
where RH is the Rydberg
constant, 2.18  10−18 J, and ni
and nf are the initial and final
energy levels of the electron.
 SAMPLE EXERCISE 6.4 Electronic Transitions in the Hydrogen Atom

Using Figure 6.13, predict which of

the following electronic transitions
produces the spectral line having the
longest wavelength: n = 2 to n = 1,
n = 3 to n = 2, or n = 4 to n = 3.

Solution The wavelength increases as frequency

decreases ( = c/ . Hence the longest wavelength
will be associated with the lowest frequency.
According to Planck’s equation, E = h, the lowest
frequency is associated with the lowest energy. In
Figure 6.13 the shortest vertical line represents the
smallest energy change. Thus, the n = 4 to n = 3
transition produces the longest wavelength (lowest
frequency) line.
PRACTICE EXERCISE
Indicate whether each of the
following electronic transitions
emits energy or requires the
absorption of energy: (a) n = 3 to
n = 1; (b) n = 2 to n = 4 .

Answers: (a) emits energy, (b) requires

absorption of energy
It absorbs energy.
Considering only the n = 1 to n = 5 states in
the hydrogen atom, which transition will emit
the most energy?

• n = 5 to n = 4
• n = 5 to n = 2
• n = 3 to n = 1
• n = 3 to n = 2
• n = 4 to n = 2
Considering only the n = 1 to n = 5 states in
the hydrogen atom, which transition will emit
the most energy?

• n = 5 to n = 4
• n = 5 to n = 2
• n = 3 to n = 1
• n = 3 to n = 2
• n = 4 to n = 2
Considering only the n = 1 to n = 5 states in
the hydrogen atom, which transition will emit
the longest wavelength?

• n = 5 to n = 4
• n = 5 to n = 2
• n = 3 to n = 1
• n = 3 to n = 2
• n = 4 to n = 2
Considering only the n = 1 to n = 5 states in
the hydrogen atom, which transition will emit
the longest wavelength?

• n = 5 to n = 4
• n = 5 to n = 2
• n = 3 to n = 1
• n = 3 to n = 2
• n = 4 to n = 2
What is the wavelength for radiation
transmitted by WGR, 550 AM (550
kHz)?
1. 0.545 m
2. 5.45 m
3. 545 m
4. 0.0018 m
5. 1.8 m
 Correct Answer:

-1
1. 0.545 m c (3.0  8
10 ms )
2. 5.45 m = =
 (5.5  5
10 s )
-1
3. 545 m
4. 0.0018 m  = 545
5. 1.8 m
Predict which of the following
electronic transitions will produce the
longest wavelength
spectral line.

1. n = 4 to n = 2
2. n = 5 to n = 2
3. n = 5 to n = 3
4. n = 6 to n = 4
 Correct Answer:

1. n = 4 to n = 2 The wavelength
2. n = 5 to n = 2 increases as frequency
3. n = 5 to n = 3
decreases. The lowest
4. n = 6 to n = 4
frequency (longest
wavelength) is
associated with the
lowest energy, and the
smallest energy
difference here is
between n = 6 and n = 4.
 Observations that led to the development of quantum mechanics
1. Hot objects emit electromagnetic radiation. (blackbody radiation)
2. Metals eject electrons when struck by a minimum frequency/energy of
electromagnetic radiation.(the photoelectric effect)
3. Excited atoms emit electromagnetic radiation of certain frequencies.
(atomic emission spectra)
Bellwork- The Photoelectric Effect
A photon with a minimum energy of 4.41x10-19J will cause emission
of an electron from sodium metal. E=hv v=6.66x1014s-1
a)What frequency and wavelength c=λν λ=4.50x10 -7m

of light does this correspond to? λ=450nm

b)What type of light is it? Visible, turquoise!

c)Describe what happens if yellow light hits sodium metal.-
Sodium electrons may absorb some photons/energy, but it is not enough to help the e escape
d)Describe what happens when UV light irradiates Na(s)
Sodium electrons may absorb some photons, and then they will have more than enough
energy to escape (n= ∞). The electron is FREE! Extra energy = KE.
 The Wave Nature of Matter
• Louis de Broglie posited that if light can
have material properties, matter should
exhibit wave properties.
• He demonstrated that the relationship
between mass and wavelength was
h
 = mv
 The Uncertainty Principle
• Heisenberg showed that the more
precisely the momentum of a particle is
known, the less precisely is its position
known: h
(x) (mv) 
4

• In many cases, our uncertainty of the

whereabouts of an electron is greater
than the size of the atom itself!
 Quantum Mechanics
• Erwin Schrödinger
developed a
mathematical treatment
into which both the
wave and particle nature
of matter could be
incorporated.
• It is known as quantum
mechanics.
 Quantum Mechanics
• The wave equation is
designated with a lower
case Greek psi ().
• The square of the wave
equation, 2, gives a
probability density map of
where an electron has a
certain statistical likelihood
of being at any given instant
in time.
 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.
Principal Quantum Number, n
• The principal quantum number, n,
describes the energy level on which the
orbital resides.
• The values of n are integers ≥ 0.
Azimuthal Quantum Number, l
• This quantum number defines the
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

Value of l 0 1 2 3
Type of orbital s p d f
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 orbital, 3 p
orbitals, 5 d orbitals, 7 f orbitals, etc.
Magnetic Quantum Number, ml
• Orbitals with the same value of n form a shell.
• Different orbital types within a shell are
subshells.
s Orbitals
• Value of l = 0.
• Spherical in shape.
• Radius of sphere
increases with
increasing value of n.
s Orbitals
Observing a graph of
probabilities of finding
an electron versus
distance from the
nucleus, we see that s
orbitals possess n−1
nodes, or regions
where there is 0
probability of finding an
electron.
 p Orbitals
• Value of l = 1.
• Have two lobes with a node between them.
d Orbitals
• Value of l is 2.
• Four of the
five orbitals
have 4 lobes;
the other
resembles a p
orbital with a
doughnut
around the
center.
What is the maximum number of orbitals
described by the quantum numbers:

n=3 l=2
• 1
• 3
• 5
• 8
• 9
What is the maximum number of orbitals
described by the quantum numbers:

n=3 l=2
• 1
• 3
• 5
• 8
• 9
What is the maximum number of electrons
described by the quantum number:
n=4
• 7
• 14
• 16
• 32
• 48
How many nodal planes does a
d orbital have?

• 0
• 1
• 2
• 3
• 4
How many nodal planes does a
d orbital have?

• 0
• 1
• 2
• 3
• 4
Which of the following is not an
allowed set of quantum numbers?

1. n = 3, l = 1, ml = 1
2. n = 3, l = 3, ml =-2
3. n = 4, l = 0, ml = 0
4. n = 3, l = 1, ml =-1
 Correct Answer:

1. n = 3, l = 1, ml = 1
2. n = 3, l = 3, ml =-2 The value of l can be
3. n = 4, l = 0, ml = 0 no larger than n - 1.
4. n = 3, l = 1, ml =-1
How many electrons maximum can
exist in the 4d orbital?

1. 2
2. 6
3. 10
4. 14
 Correct Answer:

1. 2 There are five 4d

2. 6 orbitals, each of which
3. 10
can contain up to 2
4. 14
electrons each for a
total of 10 maximum.
The electron subshell 3p represents the
principal quantum number n = ___ and
azimuthal quantum number l = ___.
1. 3; 2
2. 2; 3
3. 3; 1
4. 1; 3
 Correct Answer:

1. 3; 2
2. 2; 3 The principal quantum
3. 3; 1 number n is 3, and a p
4. 1; 3 orbital indicates l = 1.
The maximum number of electrons in
an atom that can exist in the 4f
subshell and have ml = -1 is
1. 2
2. 7
3. 14
4. 32
 Correct Answer:

1. 2
2. 7 For any value of ml,
3. 14 the maximum number
4. 32 of electrons is 2.
 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.
 Spin Quantum Number, ms
• In the 1920s, it was
discovered that two
electrons in the same
orbital do not have
exactly the same energy.
• The “spin” of an electron
describes its magnetic
field, which affects its
energy.
 Spin Quantum Number, ms
• This led to a fourth
quantum number, the
spin quantum number,
ms.
• The spin quantum
number has only 2
allowed values: +1/2
and −1/2.
 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.
Electron Configurations
• Distribution of all
electrons in an atom.
• Consist of
 Number denoting the
energy level
Electron Configurations
• Distribution of all
electrons in an atom.
• Consist of
 Number denoting the
energy level
 Letter denoting the type
of orbital.
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.
 QuickTime™ and a
Sorenson Video decompressor
are needed to see this picture.
 Orbital Diagrams
• Each box represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
arrow represents the
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.”
 Periodic Table
• We fill orbitals in
increasing order of
energy.
• Different blocks on
the periodic table,
then correspond to
different types of
orbitals.
What are the valence electrons
of vanadium?

• 4s2
• 3d3
• 4s2 3d3
• 3d5
• 4d5
What are the valence electrons
of vanadium?

• 4s2
• 3d3
• 4s2 3d3
• 3d5
• 4d5
 What are the valence electrons
of gallium?
• 4s2
• 4p1
• 4s2 3d10 4p1
• 4s2 3d10
• 4s2 4p1
 What are the valence electrons
of gallium?
• 4s2
• 4p1
• 4s2 3d10 4p1
• 4s2 3d10
• 4s2 4p1
How many unpaired electrons
does selenium have?

• 0
• 2
• 4
• 6
• 8
How many unpaired electrons
does selenium have?

• 0
• 2
• 4
• 6
• 8
The following orbital diagram
represents the electron configuration
of which element?

1s 2s 2p
1. Carbon
2. Nitrogen
3. Oxygen
4. Neon
 Correct Answer:

1s 2s 2p
1. Carbon
2. Nitrogen
3. Oxygen
4. Neon
What is the characteristic outer shell
electron configuration of the noble
gases?

1. s2p6
2. s2p5
3. s2p4
4. s2p3
 Correct Answer:

1. s2p6 Noble gases have

2. s2p5 completely filled s and
3. s2p4 p orbitals, hence their
4. s2p3
lack of reactivity.
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
copper 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.
How many unpaired electrons
does chromium have?

• 0
• 2
• 4
• 6
• 8
How many unpaired electrons
does chromium have?

• 0
• 2
• 4
• 6
• 8
Which of the following orbital
diagrams obeys Hund’s rule for a
ground-state atom?
1.
3s 3d

2.
3s 3d

3. 3s 3d
 Correct Answer:

1.
3s 3d

2.
3s 3d

3. 3s 3d