The Quantum
Mechanical Model
of the Atom
Where Are the Electrons?
We've been telling you that electrons reside in specific shells or move in
specific patterns in suborbitals. We can't really tell you exactly where an
electron is at any moment in time. We can only approximate, or guess,
where an electron is located. According to something called quantum
theory, an electron can be found anywhere around the nucleus. Using
advanced math, scientists are able to approximate the general location of
electrons. These general areas are the shells and suborbitals.
1
Bohr model of an atom
• Ex: Ti
n n
n
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n
Presentation of Lecture Outlines, 7–2
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Light has both particle & wave
behaviors
• Particle nature shown by photoelectric
effect
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Quantum Mechanics
• Quantum mechanics is the branch of
physics that mathematically describes the
wave properties of submicroscopic particles.
– We can no longer think of an electron as having a
precise orbit in an atom.
– To describe such an orbit would require knowing its
exact position and velocity.
– In 1927, Werner Heisenberg showed (from
quantum mechanics) that it is impossible to know
both simultaneously.
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Quantum Mechanics
• Heisenberg’s uncertainty principle is a
relation that states that the product of the
uncertainty in position (x) and the
uncertainty in momentum (mvx) of a particle
can be no larger than h/4.
h
( x )(m v x )
4
– When m is large (for example, a baseball) the
uncertainties are small, but for electrons, high
uncertainties disallow defining an exact orbit.
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Quantum Mechanics
Although we cannot precisely define an
electron’s orbit, we can obtain the probability
of finding an electron at a given point around
the nucleus.
Erwin Schrodinger defined this
probability in a mathematical
expression called a wave
function, denoted (psi). The
probability of finding a particle in
a region of space is defined by
.
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Four Quantum Numbers
that Describe Electrons
• According to quantum mechanics, each
electron is described by four quantum
numbers.
– Principal quantum number (n)
– Angular momentum quantum number (l)
– Magnetic quantum number (ml)
– Spin quantum number (ms)
– The first three define the wave function for a particular
electron. The fourth quantum number refers to the
magnetic property of electrons.
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Quantum #’s are like an Address.
What do you need to know to find out where you live?
State City Street House
Principle Angular Magnetic Spin Quantum #
Quantum # (n) Quantum # (l) Quantum # (ml) (ms)
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Quantum Numbers and
Atomic Orbitals
• The principal quantum number(n)
represents the “shell number” in which
an electron “resides.”
– The smaller n is, the smaller the orbital.
– The smaller n is, the lower the energy of the
electron.
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Quantum Numbers and
Atomic Orbitals
• The angular momentum quantum number
(l) distinguishes “sub shells” within a given
shell that have different shapes.
– Each main “shell” is subdivided into “sub shells.”
Within each shell of quantum number n, there are n
sub shells, each with a distinctive shape.
– l can have any integer value from 0 to (n - 1)
– The different subshells are denoted by letters.
– Letter s p d f g …
– l 0 1 2 3 4 ….
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Quantum Numbers and
Atomic Orbitals
• The magnetic quantum number (ml) distinguishes orbitals
within a given sub-shell that have different shapes and
orientations in space. Each sub shell is subdivided into
“orbitals,” each capable of holding a pair of electrons. ml can
have any integer value from -l to +l. Each orbital within a given
sub shell has the same energy.
• The spin quantum number (ms) refers to the two possible spin orientations of
the electrons residing within a given orbital. Each orbital can hold only two
electrons whose spins must oppose one another. The possible values of m s are
+1/2 and –1/2.
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Why the different shapes?
Pictures Animations
3py
s-shape 3d
s-shape
2py
p-shape p-shape
1s 2s 3s
d-shape 2px 3px d-shape
3pz
2pz d-shape
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Scanning Tunneling Microscope
Electron Clouds
Image Movie
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Figure 7.23:
Orbital
energies of
the
hydrogen
atom.
(Click here
for non-
hydrogen
atoms)
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Erwin Schrödinger
1926 -Nobel Prize in 1933
Found the probability of finding an
electron in an atom, like flies to a
candle.
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Erwin Schrödinger
1926 -Nobel Prize in 1933
Found the probability of finding an
electron in an atom, like flies to a
candle.
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The Wave Nature of Light
• A wave is a continuously repeating
change or oscillation in matter or in a
physical field. Light is also a wave.
It consists of oscillations in electric
and magnetic fields that travel
through space.Visible light, X rays,
and radio waves are all forms of
electromagnetic radiation.
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The Wave Nature of Light
A wave can be characterized by its
wavelength and frequency.
The wavelength, (lambda), is the distance between any
two adjacent identical points of a wave. The frequency,
(nyu), of a wave is the number of wavelengths that pass
a fixed point in one second.
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The Wave Nature of Light
• The product of the frequency, (waves/sec) and
the wavelength, (m/wave) would give the
speed of the wave in m/s.
– In a vacuum, the speed of light, c, is 3.00 x 108 m/s.
Therefore,
c
– So, given the frequency of
light, its wavelength can be
calculated, or vice versa.
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The Wave Nature of Light
• What is the wavelength of yellow light with a
frequency of 5.09 x 1014 s-1?
(Note: s-1, commonly referred to as Hertz (Hz)
is defined as “cycles or waves per second”.)
– If c = then rearranging, we
obtain = c/
( 3 .00 10 8 m / s ) 7
5 .09 1014 s 1
5 .89 10 m or 589 nm
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Figure 7.5: The electromagnetic
spectrum.
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end
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The Wave Nature of Light
• What is the frequency of violet light with a
wavelength of 408 nm?
– If c = then rearranging, we obtain = c/
14 1
3 .00 10 8 m / s
408 10 9 m
7 .35 10 s
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Seeing the Light-A New Model of the
Atom
Maxwell Planck-Black Body Radiation
1900—Nobel Prize in 1918
Found that blackbody
radiation was quantized.
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What is Quantized?
Energy can have only certain values (quantities),
not in between, instead of a continuum of
values. This is like energy existing on stairs of a
staircase instead of at any energy on a ramp.
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Figure 7.2:
Emission
(line)
spectra of
some
elements.
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Quantum Effects and Photons
h=Planck’s constant 6.626 x 10-34Js
hc
E= c=speed of light 3.00 x 108 m/s
ג =גwavelength of light
What is the energy of red light?
(6.626x10-34Js)(3.00x108m/s)
E=
(700x10-9m)
E= 2.84 x10-19Joules
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Einstein’s Photoelectric Effect
(1905--Nobel Prize in 1921)
Only light from a certain color (energy) could eject electrons.
Intensity of the light had no effect. Energy is absorbed only
at quantized energies!
(Animation of Photoelectron Effect) (Adsorption and Emission Spectra)
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Quantum Effects and Photons
• Photoelectric Effect
– Einstein’s assumption that an electron is ejected
when struck by a single photon implies that it
behaves like a particle.
– When the photon hits the metal, its energy, h is taken up by
the electron.
– The photon ceases to exist as a particle; it is said to be
“absorbed.”
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Quantum Effects and Photons
• Photoelectric Effect
– The “wave” and “particle” pictures of light should
be regarded as complementary views of the same
physical entity.
– This is called the wave-particle duality of light.
– The equation E = h displays this duality; E is the energy of
the “particle” photon, and is the frequency of the
associated “wave.”
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Radio Wave Energy
• What is the energy of a photon
corresponding to radio waves of
frequency 1.255 x 10 6 s-1?
Solve for E, using E = h, and four
significant figures for h.
(6.626 x 10-34 J.s) x (1.255 x 106 s-1) =
8.3156 x 10-28 = 8.316 x 10-28 J
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The Bohr Theory of the
Hydrogen Atom
1913—Nobel Prize in 1922
• Prior to the work of Niels Bohr, the stability of
the atom could not be explained using the
then-current theories.
– In 1913, using the work of Einstein and Planck, he
applied a new theory to the simplest atom,
hydrogen.
– Before looking at Bohr’s theory, we must first
examine the “line spectra” of atoms.
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The Bohr Theory of the
Hydrogen Atom
• Bohr’s Postulates
– Bohr set down postulates to account for (1) the stability of
the hydrogen atom and (2) the line spectrum of the atom.
1. Energy level postulate An electron can have only
specific energy levels in an atom.
2. Transitions between energy levels An electron in
an atom can change energy levels by undergoing a
“transition” from one energy level to another.
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The Bohr Theory of the
Hydrogen Atom
• Bohr’s Postulates
– Bohr derived the following formula for the energy
levels of the electron in the hydrogen atom.
Rh
E 2 n 1, 2, 3 ..... (for H atom)
n
– Rh is a constant (expressed in energy units) with a
value of 2.18 x 10-18 J.
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The Bohr Theory of the
Hydrogen Atom
• Bohr’s 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 h E i E f
– From Postulate 1,
Rh Rh
Ei 2 Ef 2
ni nf
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The Bohr Theory of the
Hydrogen Atom
• Bohr’s Postulates
– If we make a substitution into the previous equation that
states the energy of the emitted photon, h, equals Ei - Ef,
h E f E i
Rearranging, we obtain
( )( )
Rh
2
nf
Rh
2
ni
h R h ( 1
n f2
1
n i2
)
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The Bohr Theory of the
Hydrogen Atom
• Atomic Line Spectra
In 1885, J. J. Balmer showed that the wavelengths,
, in the visible spectrum of hydrogen could be
reproduced by a simple formula.
7 1 1
1
1 .097 10 m ( 22 n1 )
2
The known wavelengths of the
four visible lines for hydrogen
correspond to values of n = 3,
n = 4, n = 5, and n = 6.
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The Bohr Theory of the
Hydrogen Atom
• Bohr’s Postulates
– Bohr’s theory explains not only the emission of light,
but also the absorbtion of light.
– When an electron falls from n = 3 to n = 2 energy level,
a photon of red light (wavelength, 685 nm) 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.
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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.
1 1
E h R h ( 2 2 )
• Note that the sign of E is negative because energy is emitted when an electron falls from a higher to a lower level.
nf ni
E ( 2 .18 10 18
J )( 11 31 ) 2 2
18
E 1 .94 10 J
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Quantum Mechanics
• Bohr’s theory established the concept of atomic
energy levels but did not thoroughly explain the
“wave-like” behavior of the electron.
– Current ideas about atomic structure depend on
the principles of quantum mechanics, a theory
that applies to subatomic particles such as
electrons.
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Quantum Theory
of the Atom
7.4 Quantum Mechanics
7.5 Quantum Numbers and
Atomic Orbitals
Quantum Mechanics
• The first clue in the development
of quantum theory came with the
discovery of the de Broglie
1923 – Nobel Prize in 1929
relation.
– In 1923, Louis de Broglie reasoned that if light exhibits particle aspects, perhaps
particles of matter show characteristics of waves.
– He postulated that a particle with mass m and a velocity v has an associated
wavelength.
– The equation = h/mv is called the de Broglie relation.
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Quantum Mechanics
• If matter has wave properties, why are
they not commonly observed?
– The de Broglie relation shows that a baseball
(0.145 kg) moving at about 60 mph (27 m/s) has a
wavelength of about 1.7 x 10-34 m.
34 kg m 2
6.63 10 34
( 0.145 kg )( 27 m / s )
s
1.7 10 m
– This value is so incredibly small that such waves
cannot be detected.
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Quantum Mechanics
• If matter has wave properties, why are
they not commonly observed?
– Electrons have wavelengths on the order of a few
picometers (1 pm = 10-12 m).
– Under the proper circumstances, the wave character
of electrons should be observable.
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Quantum Mechanics
– In 1927, it was demonstrated that a beam of
electrons, just like X rays, could be diffracted
by a crystal.
– The German physicist, Ernst
Ruska, used this wave
property to construct the first
“electron microscope” in 1933.
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Scanning Tunneling Microscope
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Scanning Tunneling Microscope
Electron Clouds
Image Movie
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