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 Chapter 6
The Electronic
Structure of
Atoms
Chapter 2
Atoms and Elements
 The Wave Nature X-axis
of Is time
Light

Frequency and
Wavelength

c=ln

And l = c/n
c = speed of light
= 3.00 X108 m/s
 Amplitude (intensity) of a wave.

http://phet.colorado.edu/simulations/sims.php?sim=Wave_Interference
Regions of the electromagnetic spectrum.

c = ln
Sample Problem Interconverting Wavelength and Frequency

o
PROBLEM: A dental hygienist uses x-rays (l= 1.00A) to take a series of dental
radiographs while the patient listens to a radio station (l = 325 cm) and
looks out the window at the blue sky (l= 473 nm). What is the frequency
(in s-1) of the electromagnetic radiation from each source? (Assume that the
radiation travels at the speed of light, 3.00x108 m/s.)

PLAN: Use c = ln SOLUTION:

o
1.00A 10-10 m = 1.00x10-10 m
wavelength in units given o
1A 3.00x108 m/s
o = 3x1018 s-1
1 A = 10-10 m n=
1.00x10-10 m
1 cm = 10-2 m -2
1 nm = 10-9 m 325 cm 10 m = 325x10-2 m
1 cm
wavelength in m 3.00x108 m/s
n= = 9.23x107 s-1
325x10-2 m
n = c/l 10-9 m
473nm = 473x10-9 m
1 nm
frequency (s-1 or Hz) 8
n = 3.00x10 m/s = 6.34x1014 s-1
473x10-9 m
 Calculate the wavelength of red light with a
frequency of 4.62 x 1014 s1.
Given: n = 4.62 x 1014 s-1
Find: l (nm)
Conceptual n (s-1) l (m) l (nm)
Plan:
ln = c, 1 nm = 10-9 m
Relationships:
Solve:

Check: The unit is correct; the wavelength is appropriate for red

light.
Tro, Principles of Chemistry: A
8
Molecular Approach
Which of the following statements is true about
the two electromagnetic waves represented to
the right? A.
1. A has a shorter
wavelength than B
2. A has a higher B
frequency than B
3. A has a smaller 94%

amplitude than B

4% 2%

1. 2. 3.
Different
behaviors of
waves and
particles.
Amplitudes are equal
Interference
+ +
- + +
-
+ + - -
- -

+ +
- -

+ +
- -

11
The diffraction pattern caused by light
passing through two adjacent slits.

Constructive
Interference

Destructive
Interference
 Quantum Effects and Photons

By the early part of twentieth century, the wave

theory of light seemed to be well entrenched.

In 1905, Albert Einstein proposed that light had

both wave and particle properties as observed in
the photoelectric effect.
Einstein based this idea on the work of a German
physicist, Max Planck.
 Plancks Constant
Transfer of energy is quantized, and can only
occur in discrete units, called quanta.
hc
E = hn =
l
E = change in energy, in J
h = Plancks constant, 6.626 1034 J s
n = frequency, in s1
l = wavelength, in m
 Calculating the Energy of Radiation from Its
Sample Problem Wavelength
PROBLEM: A cook uses a microwave oven to heat a meal. The wavelength of
the radiation is 1.20cm. What is the energy of one photon of this
microwave radiation?
PLAN: After converting cm to m, we can use the energy equation, E = hn
combined with n = c/l to find the energy.

SOLUTION: E = hc/l
6.626X10-34J*s x 3x108m/s
E= = 1.66x10-23J
1.20cm 10-2m
cm
 Einsteins Explanation
Einstein proposed that the light energy was
delivered to the atoms in packets, called
quanta or photons.
The energy of a photon of light was directly
proportional to its frequency.
inversely proportional to its wavelength
The proportionality constant is called Plancks
constant (h) and has the value 6.626 x 10-34 Js.

Tro, Principles of Chemistry: A
16
Molecular Approach
 Calculate the number of photons in a laser pulse with
wavelength 337 nm and total energy 3.83 mJ.
Given: l = 337 nm, Epulse = 3.83 mJ
number of photons
Find:
Conceptual l(nm) l (m) Ephoton number
Plan: photons

Relationships: E = hc/l, 1 nm = 10-9 m, 1 mJ = 10-3 J, Etotal= Ephoton # photons

Solve:

10-19 J

Tro, Principles of Chemistry: A

17
Molecular Approach
What is the frequency of radiation required to supply 1.0 x
102 J of energy from 8.5 x 1027 photons?

Given: Etotal = 1.0 x 102 J, number of photons = 8.5 x 1027

Find: n
Conceptual number Ephoton n (s-1)
Plan: photons

Relationships: E = hn, Etotal = Ephoton# photons

Solve:

Tro, Principles of Chemistry: A

18
Molecular Approach
 Quantum Effects and Photons

Photoelectric Effect
The photoelectric effect is the ejection of
electrons from the surface of a metal when light
shines on it.
Electrons are ejected only if the light exceeds a
certain threshold frequency.
Violet light, for example, will cause potassium
to eject electrons, but no amount of red light
(which has a lower frequency) has any effect.
Demonstration of the
photoelectric effect.
In his explanation of the threshold frequency in the photoelectric effect, Einstein
reasoned that the absorbed photon must have the minimum energy required to dis-
lodge an electron from the metal surface. This energy is called the work function ( ,
binding energy) of that metal. What is the longest wavelength of radiation (in nm) that
could cause the photoelectric effect in the following metal: Silver, = 7.59 x 10-19 J
Use Ebinding = hn = hc/l where h = Plancks constant = 6.626 x 10-34 J.s
and c = speed of light or 3.00 x 108 m/s
7.59 x 10-19 J = (6.626 x 10-34 J.s)(3.00 x 108 m/s)/ l and
l= (6.626 x 10-34 J.s)(3.00 x 108 m/s)/(7.59 x 10-19 J) = 2.62 x 10-7 m
2.62 x 10-7 m x 109 nm/m = 2.62 x 102 nm or 262 nm
If light with a wavelength of 200 nm is used to irradiate Ag, what will be the
velocity of the ejected electron?
The binding energy listed for Ag is the minimum energy needed to eject an electron
from a silver atom. If a light with a higher frequency is strikes the surface, the
remaining energy will be converted to kinetic energy and the electron will leave
at with a higher velocity.
E = hc/l = (6.626 x 10-34 J.s)(3.00 x 108 m/s)/(2.00 x 10-7 m) = 9.94 x 10-19 J
KE = E Ebinding = (9.94 x 10-19J 7.59 x 10-19J )= 2.35 x 10-19 J. J = kg m2/s2
KE = mv2 V = (2 KE/m)1/2 = (4.70 x 10-19 J/9.11 x 10-31kg)1/2 = 7.18 x 105 m/s
 Energy and Mass
hc
Ephoton =
l
Substituting Ephoton = mphoton c2 into the above equation, we
see that mc2 = hc/l. Dividing both sides by c2 we have:
h
mphoton =
lc
(Hence the dual nature of light.)
The line spectra
of several
elements.
 1 1 1
Rydberg equation = R -
l n1 2 n22

R is the Rydberg constant = 1.096776x107 m-1

Three series of spectral lines of atomic hydrogen.

for the visible series, n1 = 2 and n2 = 3, 4, 5, ...

 The Bohr Model of the H Atom
Neils Bohr (18851962)

The nuclear model of the atom does not explain what

structural changes occur when the atom gains or loses
energy.
Bohr developed a model of the atom to explain how
the structure of the atom changes when it undergoes
energy transitions.
Bohrs major idea was that the energy of the atom is
quantized, and that the amount of energy in the atom
is related to the electrons position in the atom.
Quantized means that the atom can only have very specific
amounts of energy.

Tro, Principles of Chemistry: A

25
Molecular Approach
 Bohrs Model
The electrons travel in orbits that are at a fixed
distance from the nucleus.
stationary states
Therefore, the energy of the electron is proportional to the
distance of the orbit from the nucleus.
Electrons emit radiation when they jump from an
orbit with higher energy down to an orbit with lower
energy.
The emitted radiation is a photon of light.
The distance between the orbits determines the energy of
the photon of light produced.

Ground State: The lowest possible26stationary state for an atom (n = 1).

Tro, Principles of Chemistry: A
Molecular Approach
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Energy Changes in the Hydrogen
Atom

E = Efinal state Einitial state

E = hc
l
hc
l =
E
 Balmer
The Bohr explanation of the three series of spectral lines. Series

Energy x 10-20 J/atom

Paschen
Series

Lyman
Series

E = Efinal Einitial = (-218 x 10-20 J) (-16 x 10-20 J)

= -202 x 10-20 J
E is negative because energy leaves the atom during emission
Quantum
staircase.

E = kQ+Q-
r
 The Bohr Theory of the Hydrogen
Atom
Bohrs Postulates
Bohr derived the following formula for the energy levels
of the electron in the hydrogen atom (emission).
Rh
E 2 n 1, 2, 3 ..... (for H atom)
n
R is a constant (expressed in energy units) with
h
a value of -2.18 x 10-18 J.
Rh = 22e4/h2, where is the reduced mass of system (e & p), e is the charge on an
electron, and h is Plancks constant, 6.6256 x 10-34 Js or (kgm2/s).
If we recall that ln = c and E = hn, Rh/hc = Rrydberg
(2.18 x 10-18 J) x ( 1 ) = 1.0967 x 107 m-1
(6.626X10-34Js)(3.00 x 108 m/s)
 The Bohr Theory of the Hydrogen
Atom
Bohrs Postulates
When an electron undergoes a transition from a higher
energy level to a lower one, the energy is emitted as a
photon.

Energy of emitted photon hn ( Ef Ei )

From Postulate 1,
Rh Rh
Ei 2 Ef 2
ni nf
 The Bohr Theory of the Hydrogen
Atom
Bohrs Postulates
If we make a substitution into the previous equation
that states the energy of the emitted photon, hn,
equals Ei - Ef,

E ( E f Ei ) 2.18 x10 18 J
-18
[( ) ( )]
1
n 2f

1
ni2

Rearranging, we obtain
EH atom = -Ephoton = hn = hc/l
( )
hn Rh
1

1
n 2f ni2

1/l = -Rh/hc [( ) ( )]
1
n 2f

1
ni2
A change between two discrete energy levels
emits a photon of light.

Recall that

E = hn

and that

n = c/l
 Bohr Model of H Atoms

Tro, Principles of Chemistry: A

35
Molecular Approach
 A Problem to Consider

Calculate the energy of a photon of light emitted

from a hydrogen atom when an electron falls from
level n = 3 to level n = 1.

E hn Rh ( 1
2
1
2
n f ni
)
E (2.18 1018 J ) ( 1 1
12 32
)
18
E 1.94 10 J
 The Bohr Theory of the Hydrogen
Atom
Bohrs Postulates
Bohrs theory explains not only the emission of
light, but also the absorption of light.
When an electron falls from n = 3 to n = 2
energy level, a photon of red light (wavelength,
657nm) is emitted.
When red light of this same wavelength shines
on a hydrogen atom in the n = 2 level, the
energy is gained by the electron that undergoes
a transition to n = 3.
 Wave Behavior of Electrons
Louis de Broglie (18921987)

de Broglie proposed that particles could have a

wavelike character.
de Broglie predicted that the wavelength of a particle
is inversely proportional to its momentum.
Because it is so small, the wave character of electrons
is significant.
m = h/(cl)
s

Tro, Principles of Chemistry: A

38
Molecular Approach
 m = mass
l h /mu u = velocity
h = Plancks
constant

The de Broglie Wavelengths of Several Objects

Substance Mass (g) Speed (m/s) l (m)

slow electron 9x10-28 1.0 7x10-4

fast electron 9x10-28 5.9x106 1x10-10

alpha particle 6.6x10-24 1.5x107 7x10-15

one-gram mass 1.0 0.01 7x10-29

baseball 142 25.0 2x10-34

Earth 6.0x1027 3.0x104 4x10-63
 Sample Problem Calculating the de Broglie Wavelength of an Electron

PROBLEM: Find the deBroglie wavelength of an electron with a speed of

1.00x106m/s (electron mass = 9.11x10-31kg; h = 6.626x10-34
kg*m2/s).

PLAN: Knowing the mass and the speed of the electron allows to use the
equation l = h/mu to find the wavelength.

SOLUTION: Remember that 1 J = 1 kg-m2/s2

6.626x10-34kg*m2/s
l= = 7.27x10-10m x 109 nm/m
9.11x10-31kg x 1.00x106m/s = 0.727 nm
What is the energy associated with this electron? This energy
is in the x-ray
E = hn = hc/l= (6.626 x 10-34J-s)(3.0 x 108m/s)/(7.27 x 10-10 m ) range
= 2.7 x 10-16 J
 Electron Diffraction
Proof of the wave nature of the electron came a few
years later with the demonstration that a beam of
electrons would produce an interference pattern as if
they were waves.

If electrons behave
only like particles,
there should be only
two bright spots on the
target.
However, electrons actually
present an interference
pattern, demonstrating they
behave like waves.

41
Comparing the diffraction patterns of x-rays and electrons.

x-ray diffraction of aluminum foil electron diffraction of aluminum foil

 Uncertainty Principle
Heisenberg stated that the product of the
uncertainties in both the position and speed of a
particle is inversely proportional to its mass.
x = position, x = uncertainty in position
v = velocity, v = uncertainty in velocity
m = mass
This means that the more accurately you know the
position of a small particle, like an electron, the less
you know about its speed.
and vice versa

43
The Meaning of the Heisenberg Uncertainty Principle
We know that the electron has a mass of 9.11 x 10-31kg and moves
with an average speed of 5 x106 m/s (1.00% uncertainty)in the H atom.
The velocity is the only uncertainty in the momentum so we can calcu-
late the uncertainty in the electrons position in the H atom using
Heisenbergs Principle:

x = h/(4m v) = (6.63x10-34J-s)/[4(9.11 x 10-31kg )(5.6 x104 m/s)]

= 1 x 10-9 m (or 1 nm), where v = 0.0100 x (5.6 x 106 m/s)

The diameter of an H atom is about 0.2 nm, so the uncertainty in the

electrons position is greater than the size of the H atom! We simply
cant say where the electron is located in the H atom. Now, try
the calculation using a 70.0 kg man running at 10.0 m/s! You will find
that the uncertainty in the mans position is Very small.
 The mass of a helium atom is 4.0026 amu, and its
average velocity at 250C is 1.36 x 106 m/s. What is the
uncertainty in meters in the position of a helium atom
if the uncertainty in its velocity is 3%?
Given: 1.6606 x 10-24 g/amu, atomic weight of He is 4.003
amu. v = (0.03)(1.36 x 103 m/s) h = 6.636 x 10-34 Js
massHe = (1.6606 x 10-24 g/amu)x(4.003 amu)x(10-kg/g)
= 6.64 x 10-27 kg

Solving Heisenbergs Uncertainty Principle for x

x = h/[4 (6.64 x 10-27kg )(.03)(1.36 x 103 m/s)]

= 2 x 10-10 m
 Determinacy vs. Indeterminacy
According to classical physics, particles move in a path
determined by the particles velocity, position, and
forces acting on it.
determinacy = definite, predictable future
Because we cannot know both the position and
velocity of an electron, we cannot predict the path it
will follow.
indeterminacy = indefinite future, can only predict
probability
The best we can do is describe the probability an
electron will be found in a particular region using
statistical functions.
46
 Wave motion in
restricted systems.
 Quantum Mechanics
Based on the wave properties of the atom
H = E
= wave function
H = mathematical operator
E = total energy of the atom
The solution to an electron wave function yields four
quantum numbers that describe the energy level (shell),
the subshell or sublevel in which the electron is located,
which subshell (or sublevel) orbital is occupied by the
electron, and the spin state of the electron within the
orbital.
 Probability Distribution
Square of the wave function, 2, is the probability
of finding an electron at a given position around
the nucleus

Radial probability distribution is the probability

distribution in each spherical shell.

Many of the properties of atoms are related to

the energies of the electrons.
Electron probability in the ground-
state H atom.
 Quantum Numbers (QN) are obtained from
solutions of wave functions. They describe the
state of the electrons in the atom
An atomic orbital is specified by three quantum numbers.
1. Principal QN (n = 1, 2, 3, . . .) - related to size and energy
of the orbital. Also called the level or shell
2. Angular Momentum QN (l = 0 to n 1) - relates to shape
of the orbital. Describes the sublevel or subshell
3. Magnetic QN (ml = l to l) - relates to orientation of the
orbital in space relative to other orbitals in sublevel. Can
be observed in an external magnetic field. Gives the
number of orbitals in a sublevel.
 The Hierarchy of Quantum Numbers for Atomic Orbitals

Name, Symbol
(Property) Allowed Values Quantum Numbers

Principal, n Positive integer

1 2 3
(1, 2, 3, ...)
(size, energy)

Angular
momentum, l 0 to n-1 0 0 1 0 1 2
(shape)
l = 0 (s), l = 1 (p), l = 2 (d) l = 3 (f)
0 0 0
Magnetic, ml
-l,,0,,+l -1 0 +1 -1 0 +1
(orientation)
1 orbital
3 orbitals
-2 -1 0 +1 +2

5 orbitals
Sample Problem Determining Quantum Numbers for an Energy Level

PROBLEM: What values of the angular momentum (l) and magnetic (ml)
quantum numbers are allowed for a principal quantum number (n)
of 3? How many orbitals are allowed for n = 3?
PLAN: Follow the rules for allowable quantum numbers found in the text.
l values can be integers from 0 to n-1; ml can be integers from -l
through 0 to + l.
SOLUTION: For n = 3, l = 0, 1, 2

For l = 0 ml = 0

For l = 1 ml = -1, 0, or +1

For l = 2 ml = -2, -1, 0, +1, or +2

There are 9 ml values and therefore 9 orbitals with n = 3.

Sample Problem Determining Sublevel Names and Orbital Quantum Numbers

PROBLEM: Give the name, magnetic quantum numbers, and number of

orbitals for each sublevel with the following quantum numbers:
(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3

PLAN: Combine the n value and l designation to name the sublevel.

Knowing l, we can find ml and the number of orbitals.

SOLUTION:
n l sublevel name possible ml values # of orbitals

(a) 3 2 3d -2, -1, 0, 1, 2 5

(b) 2 0 2s 0 1

(c) 5 1 5p -1, 0, 1 3
(d) 4 3 4f -3, -2, -1, 0, 1, 2, 3 7
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 node
nodes

Nodes are areas where there should be no electrons. The number of nodes increases
with increasing orbital energy.
 The 2p orbitals.

atomic orbital,

Probability of finding electron

2
The 3d orbitals.
3 d orbitals, contd
One of the seven
possible 4f orbitals.
 A Summary of the H Atom
In the quantum (wave) mechanical model, the electron is a standing
wave and can be described by a series of wave functions (orbitals)
That describe the possible energies and spatial distributions available
to the electron.
From the Heisenberg Uncertainty Principle, the model cannot predict
the exact electron motions the 2 represents the probability distri-
bution of the electrons in that orbital. We depict the orbital as an
electron density map.
The size of an orbital is arbitrarily defined as the surface that contains
90% of the total probability of finding an electron (electron density).
The H atom has many types of orbitals in the ground state, the single
electron resides in the 1s orbital. The electron can be excited to higher
energy orbitals if the appropriate amount of energy is put into the
atom. When an excited electron falls to ground state, a photon is
emitted with energy equal to the difference between the final and initial
energy states of the electron
Summary of Quantum Numbers of Electrons in Atoms

Name Symbol Permitted Values Property

principal n positive integers(1,2,3,) orbital energy (size) Shell

angular l integers from 0 to n-1 orbital shape (The l values 0,

momentum 1, 2, and 3 correspond to s, p,
d, and f orbitals, respectively.)
Subshell
magnetic ml integers from -l to 0 to +l orbital orientation
For l = 3, the values for ml are -3, -2, -1, 0, +1, +2, +3
spin ms +1/2 or -1/2 direction of e- spin
or s
Observing the effect of electron spin.

The Stern-Gerlach experiment.

A representation of electron spin.
 Pauli Exclusion Principle
As a result, each orbital can hold 2 electrons
(will have the same n, l, ml), and the electrons
occupying the same orbital must have
opposing spins (-1/2, +1/2), or different values
for ms.
In a given atom, no two electrons can have the
same set of four quantum numbers (n, l, ml,
ms).
 Electron Configuration
An electron configuration of an atom is a
particular distribution of electrons among available
sub shells.
The notation for a configuration lists the sub-
shell symbols sequentially with a superscript
indicating the number of electrons occupying
that sub shell.
For example, lithium (atomic number 3) has
two electrons in the 1s sub shell and one
electron in the 2s sub shell 1s2 2s1.
1s^22s^1 for MC
 Order for filling energy sublevels with
electrons.

Illustrating Orbital Occupancies

To write the electron configuration

Energy
level #of electrons in the sublevel
n l
s,p,d,f
1s2
The orbital diagram (box or circle)
The effect of orbital shape.
 A vertical orbital diagram for the Li ground state.

no color-empty

Li (Z = 3) light - half-filled
electron
configuration:
1s22s1

dark - filled, spin-paired

 Hunds Rule

The lowest energy configuration

for an atom is the one having the
maximum number of unpaired
electrons allowed by the Pauli
principle in a particular set of
degenerate orbitals (subshell).
 A vertical orbital diagram for the C ground state.

Light half-filled
no color-empty

C (Z = 6)
electron
configuration:
1s22s22p2

dark - filled, spin-paired

Sample Problem Determining Quantum Numbers from Orbital
Diagrams
PROBLEM: Use the periodic table to identify the neutral element with the
electron configuration 1s2 2s2 2p5 . Write a set of quantum numbers
for the third electron and a set for the eighth electron of the atom.
PLAN: Use the orbital diagram to find the third and eighth electrons.
The element has 9 electrons, so the element is F

9F

1s 2s 2p
SOLUTION: The third electron is in the 2s orbital. Its quantum numbers are

n= 2 l= 0 ml = 0 ms= + 1/2

The eighth electron is in a 2p orbital. Its quantum numbers are

n= 2 l= 1 ml = 0 (-1, 0, +1) ms= -1/2

Hunds rule

Filled d
 Filled pseudocore

Noble gas configuration + filled d orbitals = pseudocore

 The relation between orbital filling and the periodic
table.

ns np
(n 1) d

(n 2) f
 A diagram that summarizes
the order in which the orbitals fill in
polyelectronic atoms.
 What is the correct orbital diagram for a N
atom (Z = 7)?

1s 2s 2px 2py 2pz

16%
A. _ ____
B.81% __ __ __
C.3% _ ___
SAMPLE PROBLEM Determining Electron Configuration

PROBLEM: Using the periodic table on the inside cover of the text, give the full and
condensed electrons configurations, partial orbital diagrams showing
valence electrons, and number of inner electrons for the following
elements:
(a) potassium (K: Z = 19) (b) molybdenum (Mo: Z = 42) (c) lead (Pb: Z = 82)
PLAN: Use the atomic number for the number of electrons and the periodic table
for the order of filling for electron orbitals. Condensed configurations
consist of the preceding noble gas and outer electrons.
SOLUTION:
(a) for K (Z = 19)

full configuration 1s22s22p63s23p64s1

condensed configuration [Ar] 4s1

partial orbital diagram There are 18 inner electrons.

4s1 3d 4p
SAMPLE PROBLEM

continued
(b) for Mo (Z = 42)
full configuration 1s22s22p63s23p64s23d104p65s14d5
condensed configuration [Kr] 5s14d5
partial orbital diagram There are 36 inner electrons
and 6 valence electrons.

5s1 4d5 5p
(c) for Pb (Z = 82)
full configuration 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2

condensed configuration [Xe] 6s24f145d106p2

partial orbital diagram
There are 78 inner electrons
and 4 valence electrons.

Do not include filled set of d and/or f

6s2 6p2
orbitals as part of valence electrons!
 Valence Electrons
The electrons in the outermost principle
quantum level (n) of an atom.

Atom Valence Electrons

[Ar] 4s2
Ca 2
[He] 2s22p3
N 5
[Ar] 3d10 4s24p5
Br 7
Sc 3 [Ar]4s 3d2 1

Inner electrons are called core electrons.

Core electrons include noble gas config-
urations + any filled d and f subshells.
 Broad Periodic Table Classifications
Representative Elements (main group): filling s
and p orbitals (Na, Al, Ne, O)
Transition Elements: filling d orbitals (Fe, Co,
Ni)
Lanthanide and Actinide Series (inner
transition elements): filling 4f and 5f orbitals
(Eu, Am, Es)
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 s-block p-block

1 A periodic table of partial ground-

state electron configurations
2
(n-1) d-block
3

(n-2) f-block