Chapter 8: The Quantum

Mechanical Atom
• By the late 1800’s it was clear that classical
physics was incapable of describing atoms and
molecules
• Experiments showed that electrons acted like tiny
charged particles in some experiments and waves
in others
• The physics that describes objects with
wave/particle duality is called quantum
mechanics or quantum theory
• Energy can be transferred between things as
light or radiation
• Radiation carries energy through space as
waves or oscillations moving outward from
a disturbance
• Electromagnetic waves (radiation) may be
characterized by their “height” or
amplitude and the number that occur per
second or frequency (v)
• The units of frequency are the hertz (Hz)
1 Hz = 1 s -1 = 1 / s = 1 /(second)
• The minimum and maximum amplitude of
electromagnetic radiation are evenly spaced
• The peak-to-peak distance is called the
wavelength (λ )
• The product of frequency and wavelength
give the speed of light (c)
λ × υ = c = 3.00 × 108 m/s
• Electromagnetic radiation comes in a broad
range of frequencies called the
electromagnetic spectrum
• The electromagnetic spectrum is divided
into regions according to the wavelengths
of radiation
• What we call light is a small slice of the
electromagnetic spectrum with wavelengths
between about 400 and 700 nm
• This is called the visible region because we can
“see” these wavelengths of the electromagnetic
spectrum
• Gamma rays, X rays, and ultraviolet radiation
have wavelengths shorter than the visible region
• Microwaves, infrared radiation, and radio waves
have wavelengths longer than visible light
• The way a substance absorbs
electromagnetic radiation can be used to
characterize it
• For example, each substance absorbs a
uniquely different set of infrared
frequencies
• A plot of wavelengths absorbed versus the
absorption is called an infrared absorption
spectrum
• It can be used to identify a substance
 Infrared
absorption
spectrum of
wood
alcohol
(methanol).

• The oscillating magnetic and electric fields

of an electromagnetic wave interact with
particles that it passes
• A charged particle can pick up energy at the
expense of the radiation source
• The energy transfer is not describe correctly
by classical physics
• In 1900 the German scientist Max Planck
proposed that the electromagnetic radiation
could be viewed as a stream of tiny energy
packets or quanta we now call photons
• Photons travel at the speed of light
• Planck proposed, and Einstein confirmed,
that the energy of a photon is proportional
to its frequency
 energy of photon = E = hν
h = Planck' s constant = 6.626 × 10 -34 Js
• This means that both electrons and
electromagnetic radiation can be
represented as either waves or particles
• The visible spectrum is a continuous
spectrum because it contains a continuous
distribution of light of all colors
• Excited atoms can emit light
• The atomic spectrum or emission
spectrum is a series of individual lines
called a line spectrum
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

• In general, the line spectrum of an element
is rather complicated
• The line spectrum of hydrogen, with a
single electron, is the simplest
• The Rydberg equation can be used to
calculated all the spectral lines of hydrogen
1
λ =R ( − )
1
H n2
1
n22
1

• n1 and n2 are positive integers

• The Rydberg constant, RH, is an empirical
constant with a value of 109,678 cm-1
• Atomic line spectra tells us that when an
excited atom loses energy, not just any
arbitrary amount can be lost
• This is possible if the electron is restricted
to certain energy levels
• The energy of the electron is said to be
quantized
 Continuous (a) and discrete
(b) potential energy of a
tortoise. The potential
energy of the tortoise in (b)
is quantized.

• The first theoretical model that successfully

accounted for the Rydberg equation was
proposed in 1913 by Niels Bohr
• Bohr proposed that the electrons moved
around the nucleus is fixed paths or orbits
much like the planets move around the sun
• The orbits, labeled with the integer n, have
energy
E = − n 2 h 2 = − nb2
2π 2 me 4

−18
b= 2π 2 me 4
h2
= 2.18 ×10 J
• This equation allows the calculation of the
energy of any orbit
 Absorption and emission
of energy by the hydrogen
atom. An electron that
absorbs energy is raised to
a higher energy level. A
particular frequency of
light is emitted when an
electron falls to a lower
energy level.
• The lowest energy state of an atom is called
the ground state (an electron with n = 1 for
a hydrogen atom)
• An electron that “escapes” from the nucleus
has infinity for its quantum number and
zero energy
• Bohr’s (theoretical) equation explains the
(empirical) Rydberg equation
∆E = Eh − El = ( −b
nh2
− −b
nl2
)
=b ( 1
nl2
− n12 ) with nh > nl
( )
h

= hc( 1
λ ) or 1
λ = b 1
hc nl2 − n12
h
• The combination of constants, b/hc, has a
value which differs from the experimentally
derived value of RH by only 0.05%
• Bohr’s efforts to develop a general theory
of electronic structure was doomed by the
wave/particle duality of electrons
• De Broglie suggested that the wavelength of
a particle of mass m moving at speed v is
λ= h
mv
• This relation provides the link between the
description as a particle and as a wave
• Heavy objects have very “short”
wavelengths so their matter waves and the
wave properties go unnoticed
• Tiny particles with small masses have
“long” wavelengths so their wave properties
are an important part of their behavior
• Waves combine in two ways
(a) Waves in phase interfere constructively. (b) Out of phase
waves produce destructive interference. (c) Waves passing
through holes fan out and produce an interference pattern.

• The constructive and destructive

interference is called diffraction
• Electrons produce similar patterns
• There are two types of waves: traveling
and standing
The 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
• Points of zero wave amplitude are called
nodes
 Standing waves on a guitar string.

• For guitar strings the only waves 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
L = n( λ2 ) or rearranging : λ = 2L
n
• These results can be used to show how
quantum theory unites the wave and particle
description of a bound electron
• Consider the classical particle model of the
“bead on a wire”
• If the electron (particle) has mass m and
speed v
• The kinetic energy of the moving electron is
E = mv
1
2
2
 (a) A classical model of the
electron as a bead on a wire.
Any energy is possible and
position is exactly known. (b)
Classical model of the electron
as a standing wave. (c) Quantum
mechanical model combines (a)
and (b). Dark areas indicate
probable electron positions.

• The De Broglie relation connects models (a)

and (b)
 λ= h
mv or v = h
mλ substituting :
E = mv = m(
1
2
2 1
2
h 2
mλ
) = h2
2 mλ2

using λ = 2L
n gives E = n 2 h2
8 mL2
– The electron energy is quantized because it
depends on the integer n
– The lowest energy allowed is for n=1 or
E=h2/8mL2 (the energy cannot be zero)
• Electrons trapped on a wire have some
residual kinetic energy, just like electrons
trapped in atoms

The spacing between

levels is proportional to
1/L2. (a) A long wire.
(b) A short wire. The
longer the wire, the
smaller the spacing
between allowed energy
levels.
• The wave that corresponds to the electron is
called a wave function
• The 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
• Regions of zero wave function amplitude
are called nodes
• It is generally true that the more nodes an
electron has, the higher its energy
• Erwin Schrödinger was the first to
successfully apply the concept of the wave
nature of matter to electronic structure
• He developed an equation that can be
solved to give wave functions and energy
levels for electrons trapped in them
• Wave functions for electrons in atoms are
called orbitals
• Orbitals are characterized by a set of three
quantum numbers:
n = principle quantum number. All orbitals with the
save principle quantum number are in the same
shell. Allowed values: the set of positive integers.
l = secondary quantum number which divides the
orbitals in a shell into smaller groups called
subshells. Allowed values: from 0 to (n – 1).
ml = magnetic quantum number which divides the
subshells into individual orbitals. Allowed values:
integers from –l to +l.
Relationships between n, l, and ml.
Number of
n l ml Subshell Orbitals
1 0 0 1s 1
2 0 0 2s 1
1 -1, 0, 1 2p 3
3 0 0 3s 1
1 -1, 0, 1 3p 3
2 -2, -1, 0, 1, 2 3d 5
4 0 0 4s 1
1 -1, 0, 1 4p 3
2 -2, -1, 0, 1, 2 4d 5
3 -3, -2, -1, 0, 1, 2, 3 4f 7
• The approximate energies of the subshells
in an atom with more than one electron:

The quantum
numbers associated
with the first two
shells are shown.

• Electrons behave like tiny magnets

• Electrons within atoms interact with a
magnet field in one of two ways:
Electrons can spin in either
direction in the presence of an
external magnetic field. This
gives rise to the spin quantum
number, ms with allowed
values of +1/2 (spin “up”) or
–1/2 (spin “down”).
• Electron spin is important in determining
electronic structure
• According to the Pauli exclusion principle
no two electrons in the same atom can have
identical values for all four quantum
numbers
• Thus two electron can occupy the same
orbital only if they have opposite spin and
are said to be paired
• A substance with more spin in one direction
is said to contain unpaired electrons
• Substances with unpaired electrons are
slightly attracted to a magnet and are called
paramagnetic
• Substances in which all electrons are paired
are called diamagnetic
• The distribution of electrons among the
orbitals of an atom is called the electronic
structure or electronic configuration
• To indicate the ground state electron
configuration we can:
1) List the subshells that contain electrons and
indicate their electron population with a
superscript.
2) Represent each orbital with a circle and use
arrows to indicate the spin of each electron.
• Electron configurations must be consistent
with the Pauli principle, aufbau principle,
and Hund’s rule
Example: N 1s22s22p3, Na 1s22s22p63s1
• Electron configurations explain the
structure of the periodic table
The periodic table is
divided into regions of
2, 6, 10, and 14
columns which is the
maximum number of
electrons in s, p, d, and
f sublevels.

Subshells that fill

across the periods.
• 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
• For these elements the valence electrons
consist of just the s and p subshells
encountered crossing the period that
contains the element in question
Example: the valence configuration of bromine is
Br 4s24p5
• There are few important exceptions to the
“expected” electronic figurations of
commonly encountered elements
• Following the rules for Cr, Cu, Ag, and Au
using noble gas notation:
Element Expected Experimental
Cr [Ar]3d 4 4 s 2 [Ar]3d 5 4 s1
Cu [Ar]3d 9 4 s 2 [Ar]3d 10 4 s1
Ag [Kr]4d 9 5s 2 [Kr]4d 10 5s1
Cu [Xe]5d 9 6 s 2 [Xe]5d 10 6 s1
• Apparently, half-filled and filled subshells
are particularly stable
• Similar irregularities occur among the
lanthanide and actinide elements
• The position of an electrons must be
described with probabilities
• Heisenberg’s uncertainty principle says
that it is impossible to measure with
complete precision the velocity and
position of a particle simultaneously
• These limitations are not important for large
objects but are very important for small
particles like electrons
• Quantum mechanics requires that we talk
about the probability of finding an electron
in a particular region of space
• This probability is often represented as an
electron cloud about the nucleus
• The probability varies with distance from
the nucleus
 (a) A dot-density
diagram for an
electron in a 1s
orbital. (b) Graph
of probability
versus distance.

• This type of plot shows that electron

density varies from place to place
• Electron density variations define the shape,
size, and orientation of orbitals
 Orbitals get larger as the
principle quantum number n
increases. Nodes, or regions
of zero electron density,
appear beginning with the
2s orbital.

• p orbitals are quite different from s orbitals

• They posses a nodial plane which includes
the nucleus and 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.
• Recall that there are three different orbitals
in each p subshell
The directions of maximum
electron density lie along lines that
are mutually perpendicular. It is
convenient to label the orbitals as
px, py, and pz
• The shape and orientation of d orbitals are
more complicated than for p orbitals

Shape and directional properties of the five d orbitals

in a d subshell.
• The f orbitals are even more complex than
the d orbitals
• The amount of positive charge “felt” by
outer electrons in atoms other than
hydrogen is called the effective nuclear
charge
• It is lower than the atomic number because
of shielding
If the 2- charge of the 1s2 core
of lithium were 100%
effective at shielding the 2s
electron from the nucleus, the
valence electron would “see”
a charge of +1.
• The effective nuclear charge felt by outer
electrons is determined primarily by the
difference between the charge on the
nucleus and the charge on the core
• Effective nuclear charge controls a number
of properties
– Atomic size increases top to bottom in a group
because of increasing n and gets smaller left to
right in a groups because the effective nuclear
charge increases
• Variation in atomic and ionic radii. Values
in picometers (10-12 m)
• The size trends in ions can be summarized:
– Positive ions are always smaller than the atoms
they are formed
– Negative ions always larger than the atoms
from which they are formed

Adding electrons leads to an

increase in size of a particle, as
illustrated for fluorine.
Removing electrons decreases
the size of the particle, as shown
for lithium and iron.
• Ionization energy (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
• The trends in IE are the opposite of the
trends in atomic size
Variations in first
ionization-energies.
Elements with the
largest ionization
energies are in the
upper right of the
periodic table.
Those with the
smallest ionization
energy are at the
lower left.
Variations in
successive
ionization
energies. Note
that it is
extremely
difficult to
break into the
noble gas core
(2nd through 8th
ionizations for
Li through F,
respectfully.
• The 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)
• The addition of one electron to a neutral
atom is exothermic for nearly all atoms
• The addition of more electrons requires
energy
• 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-

• The results for first electron affinities can

be generalized
• In general:
– EA increases from left to right in a period
– EA increases bottom to top in a group