The Electronic Structures of Atoms

Electromagnetic Radiation

z The wavelength of electromagnetic radiation

has the symbol λ .
z Wavelength is the distance from the top (crest)
of one wave to the top of the next wave.
• Measured in units of distance such as m,cm, Å.
• 1 Å = 1 x 10-10 m = 1 x 10-8 cm
z The frequency of electromagnetic radiation
has the symbol υ.
z Frequency is the number of crests or troughs
that pass a given point per second.
• Measured in units of 1/time - s-1
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Electromagnetic Radiation

z The relationship between wavelength and

frequency for any wave is velocity = λ υ.
z For electromagnetic radiation the velocity is 3.00 x
108 m/s and has the symbol c.
z Thus c = λ υ for electromagnetic radiation.

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Electromagnetic Radiation
z Molecules interact with electromagnetic
radiation.
• Molecules can absorb and emit light.
z Once a molecule has absorbed light
(energy), the molecule can:
1.Rotate
2.Translate
3.Vibrate
4.Electronic transition
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Electromagnetic Radiation
z What is the frequency of green light of
wavelength 5200 Å?
c
c = λν ∴ ν =
λ
 1 x 10-10 m 
(5200 Å)   = 5.200 × 10-7 m
 1Å 
3.00 × 108 m/s
ν=
5.200 × 10-7 m
ν = 5.77 × 1014 s -1
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Electromagnetic Radiation
z In 1900 Max Planck studied black body
radiation and realized that to explain the
energy spectrum he had to assume that:
1.Energy is quantized
2.Light has particle character
z Planck’s equation is
hc
E = h ν or E =
λ
h = Planck’ s constant = 6.626 x 10 -34
J ⋅s
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Electromagnetic Radiation
z What is the energy of a photon of green light
with wavelength 5200 Å? What is the energy
of 1.00 mol of these photons?
We know that ν = 5.77 x 1014 s -1
E = hν
E = (6.626 × 10 -34 J ⋅ s)(5.77 × 1014 s -1 )
E = 3.83 × 10 -19 J per photon
For 1.00 mol of photons :
(6.022 × 10 23 photons)(3.83 × 10 -19 J per photon) = 231 kJ/mol
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Atomic Spectra and the Bohr
Atom
z An emission spectrum is formed by an
electric current passing through a gas in a
vacuum tube (at very low pressure) which
causes the gas to emit light.
• Sometimes called a bright line spectrum.

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Atomic Spectra and the Bohr
Atom
z An absorption spectrum is formed by
shining a beam of white light through a
sample of gas.
• Absorption spectra indicate the wavelengths of light
that have been absorbed.

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Atomic Spectra and the Bohr
Atom
z Every element has a unique spectrum.
z Thus we can use spectra to identify
elements.

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Atomic Spectra and the Bohr
Atom
z An orange line of wavelength 5890 Å is
observed in the emission spectrum of sodium.
What is the energy of one photon of this
orange light?
 1 × 10 m 
-10
λ = 5890 Å   = 5 .890 × 10 − 7 m
 Å 
hc
E = hν =
λ
=
(6 .626 × 10 − 34
)(
J ⋅ s 3 .00 × 10 8 m/s )
5 .890 × 10 − 7 m
= 3 .375 × 10 −19 J
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Gold complexes under UV or “black” light
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 Atomic Spectra and the Bohr
Atom
1  1 1 
= R  2 − 2 
z The Rydberg equation λ  n1 n 2 
is an empirical R is the Rydberg constant
equation that relates
R = 1.097 × 107 m -1
the wavelengths of the
n1 < n 2
lines in the hydrogen
spectrum. n’ s refer to the numbers
of the energy levels in the
emission spectrum of hydrogen
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Atomic Spectra and the Bohr
Atom
z What is the wavelength of light emitted
when the hydrogen atom’s energy
changes from n = 4 to n = 2?
n 2 = 4 and n1 = 2
1  1 1 
= R  2 − 2 
λ  n1 n 2 
1  1 1
= 1.097 × 107 m -1  2 − 2 
λ 2 4 
1 -1  1 1
= 1.097 × 10 m  − 
7

λ  4 16 
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 Atomic Spectra and the Bohr
Atom
1
Notice that the wavelength = 1.097 × 107 m -1 (0.250 − 0.0625)
λ
calculated from
1
the Rydberg equation = 1.097 × 10 7 m -1 (0.1875)
λ
matches the wavelength
1
of the green colored line in = 2.057 × 106 m -1
λ
the H spectrum.
λ = 4.862 ×10-7 m

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Atomic Spectra and the Bohr
Atom
z In 1913 Neils Bohr incorporated Planck’s
quantum theory into the hydrogen spectrum
explanation.
z Here are the postulates of Bohr’s theory.
1. Atom has a number of definite and discrete
energy levels (orbits) in which an electron
may exist without emitting or absorbing
electromagnetic radiation.
As the orbital radius increases so does the energy
1<2<3<4<5......
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Atomic Spectra and the Bohr
Atom
2. An electron may move from one discrete
energy level (orbit) to another, but, in so doing,
monochromatic radiation is emitted or
absorbed in accordance with the following
equation. hc
E 2 - E1 = ∆E = hν =
λ
E 2 > E1
Energy is absorbed when electrons jump to higher orbits.
n = 2 to n = 4 for example
Energy is emitted when electrons fall to lower orbits.
n = 4 to n = 1 for example
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Atomic Spectra and the Bohr
Atom

3. An electron moves in a circular orbit about the

nucleus and it motion is governed by the ordinary
laws of mechanics and electrostatics, with the
restriction that the angular momentum of the
electron is quantized (can only have certain
discrete values).

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 Atomic Spectra and the Bohr
Atom

z Light of a characteristic wavelength (and

frequency) is emitted when electrons move
from higher E (orbit, n = 4) to lower E (orbit,
n = 1).
• This is the origin of emission spectra.
z Light of a characteristic wavelength (and
frequency) is absorbed when electron jumps from
lower E (orbit, n = 2) to higher E (orbit, n= 4)
– This is the origin of absorption spectra.
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Atomic Spectra and the Bohr
Atom

z Bohr’s theory correctly explains the H

emission spectrum.
z The theory fails for all other elements
because it is not an adequate theory.

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The Wave Nature of the Electron
z In 1925 Louis de Broglie published his Ph.D.
dissertation.
• A crucial element of his dissertation is that
electrons have wave-like properties.
• The electron wavelengths are described by the
de Broglie relationship. h
λ=
mv
h = Planck’ s constant
m = mass of particle
v = velocity of particle

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The Wave Nature of the Electron
z De Broglie’s assertion was verified by
Davisson & Germer within two years.
z Consequently, we now know that
electrons (in fact - all particles) have
both a particle and a wave like character.
• This wave-particle duality is a fundamental
property of submicroscopic particles.

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The Wave Nature of the Electron
z Determine the wavelength, in m, of an electron,
with mass 9.11 x 10-31 kg, having a velocity of
5.65 x 107 m/s.
• Remember Planck’s constant is 6.626 x 10-34 Js which is
also equal to 6.626 x 10-34 kg m2/s2.
h
λ=
mv
6.626 ×10−34 kg m 2 ⋅ s 2
λ=
( )(
9.11×10-31 kg 5.65 ×107 m/s )
λ = 1.29 ×10−11 m
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The Quantum Mechanical
Picture of the Atom
z Werner Heisenberg in 1927 developed the
concept of the Uncertainty Principle.
z It is impossible to determine simultaneously
both the position and momentum of an
electron (or any other small particle).
• Detecting an electron requires the use of
electromagnetic radiation which displaces the
electron!
• Electron microscopes use this phenomenon
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The Quantum Mechanical
Picture of the Atom

z Consequently, we must must speak of the

electrons’ position about the atom in terms
of probability functions.
z These probability functions are
represented as orbitals in quantum
mechanics.

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The Quantum Mechanical
Picture of the Atom
Basic Postulates of Quantum Theory
1. Atoms and molecules can exist only in
certain energy states. When an atom or
molecule changes its energy state, it
must emit or absorb just enough energy
to bring it to the new energy state (the
quantum condition).

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The Quantum Mechanical
Picture of the Atom
2. Atoms or molecules emit or absorb
radiation (light) as they change their
energies. The frequency of the light
emitted or absorbed is related to the
energy change by a simple equation.
hc
E = hν =
λ

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The Quantum Mechanical
Picture of the Atom

3. The allowed energy states of atoms and

molecules can be described by sets of
numbers called the four quantum numbers.
z Quantum numbers are the solutions of the
Schrodinger, Heisenberg & Dirac equations.
..
Schr o dinger equation
b2  ∂ 2Ψ ∂ 2Ψ ∂ 2Ψ 
− 2  2 + 2 + 2  + VΨ = EΨ
8π m  ∂ x ∂ y ∂ z 

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