Atomic structure

Chapter 5: Electrons in Atoms The product of frequency and wavelength for all forms of
Light (Electromagnetic Radiation) electromagnetic radiation (light) is a constant, the speed of light
• Light has the properties of both waves and particles. “c”.
• Light waves carry energy through space.
frequency and wavelength are
wavelength (λ) meters inversely related:
frequency (ν) Hz (s-1) ë×õ=c
amplitude (a) intensity high frequency corresponds to
c c
õ= and ë= short wavelength
All light travels at the same speed, ë õ long wavelength corresponds to
c = 2.99792 x 10 8 m/sec (vacuum) low frequency

The frequency (ν is pronounced “nu”) is the number of

wavelengths that pass a point in a given period of time.
(cycles per second) or s-1 where 1Hz = 1s-1

The wavelength (λ is pronounced “lambda”) is the distance

between wave crests in meters
(m, cm, nm, pm, Å (angstrom, 10-10 m))

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 Atomic structure
The Electromagnetic Spectrum

Example:
What wavelengths correspond to FM radio (MHz) signals? What frequencies correspond to microwaves?

ë ×õ = c ë×õ=c
c c
ë= õ=
õ ë
3.00 × 108 m 3.00 × 10 8 m s
ë= s = 3.21 m õ= = 3.00 × 1014 Hz = 3.00 × 108 Mz
10 Hz 1s− 1
6
1 × 10− 6 m
93.5 MHz × × 1 ìm ×
1 MHz Hz 1 ìm

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 Atomic structure
Properties of waves: “Ultraviolet Catastrophe”
(a) Constructive inference:
When waves that are in phase interact, they do so such that Classically, the intensity of light should increase with decreasing
the amplitudes add in a positive manner. wavelength.

If this were so, the intensity of UV light would go to infinity with

decreasing wavelength.
(b) Destructive Interference:
When waves that are out of phase interact, they do so such that the I order to explain the observations of black-body radiation, Planck
amplitudes cancel one another. surmised that light is released in defined packets or quanta.

Light and Energy: Planck’s Law

Planck’s Law: Energy is discontinuous; the transmission of

energy can only occur in finite amounts or “Quanta”

Ephoton = h⋅ν h = Planck’s constant = 6.626 x 10-34 J⋅s

Planck’s Law is based on the phenomenon known as the

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 Atomic structure
As the frequency of light increases, the energy increases. Bond energies also correspond to the energies of individual
photons. The process of light breaking chemical bonds is known as
As the wavelength of light increases, the energy decreases. photodissociation.

hc
E photon = h ⋅ν =
λ

Red Light (650 nm)

hc 6.626 × 10 Js × 3.00 × 10 m s
-34 8
J
E photon = = = 3.06 × 10-19
ë 1m photon
650 nm × 9
10 nm

Blue Light (400 nm) kJ 1 mol H 2

435.93 × ×
mol 6.022x10 23 H 2
hc 6.626 × 10 Js × 3.00 × 10 m s
-34 8
J
E photon = = = 4.97 × 10-19
ë 1m photon 10 3 J
400 nm × 9 H2
× = 7.24 x 10 -19
J
10 nm photon kJ photon
Calculate the energy of a mole of photons of 400 nm light.
hc hc
E photon = ë=
m
hc 6.626 × 10 J ⋅ s × 3.00 × 10
-34 8
ë E photon
s × 6.022 × 10 photons =
23
E photon = =
ë 1m mole photons
400 nm × 9
10 nm 6.626 × 10 - 43 J ⋅ s × 3.00 × 108 ms -1
ë=
J
7.24 x 10-19
J photon
2.99 × 10 5
mole photons
= 2.75 × 10 -7 m or 275 nm

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 Atomic structure
Quantum Theory: Atomic Spectra:

Atomic Spectrum

When a discharge is passed through a tube filled with He, the light emitted spreads into a series of
lines rather than a normal spectrum of light.

This indicates that something in the atom is not governed by a continuum…

Something is Quantized!

Recall that Quantization was used to explain the “Ultraviolet Catastrophe” (Planck)

Einstein’s work on the “Photoelectric Effect” also contributed to the concept of quantization.

When light strikes the surface of certain metals, electrons may be ejected.

The light must be of a certain frequency (color) in order for this to occur.

The behavior exhibits a threshold effect such that below a minimum energy, no electrons are
ejected.

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 Atomic structure
The threshold behavior for the “Photo-electric Effect”
ν (photon) = νo electrons are removed with no KE
Since E = hν
ν (photon) > νo electrons are ejected
Only photons of frequency greater than the minimum frequency
(νo) can eject electrons Example:
Any excess energy from the photon goes into the kinetic energy of
the electron. A certain metal has a threshold frequency (νo) of 3.66 x 10 -14 s-1.

Will 532 nm light cause electrons to be ejected?

E (electron) = E (photon) - Φ

if ν (photon) > νo then electrons are ejected

ν⋅λ = c

m
E (electron) = E (photon) - Φ = ½ mev2 3.00 × 108
c s
í = = = 5.64 × 14 s-1
ë 532 nm x m
10 9 nm
E (photon) = hν
me = 9.11 x 10-31 kg
ν (photon) > νo Electron are ejected
v = velocity of the ejected electrons
Φ = ejecton threshold “Work function” What is the velocity of the ejected electrons?
νo = Φ/h “Threshold frequency”
E (electron) = E (photon) - Φ = ½ mev2
If…

ν (photon) < νo no electrons are ejected

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 Atomic structure
1 hc The Bohr Atom:
mev 2 = - hí o
2 ë
The concept of the atom derived form the Rutherford gold film
experiment failed to explain hoe the electrons ordered them selves
m about the nucleus.
6.626 x 10 - 34 J ⋅ s x 3.00 x 108
hc s = 3.74 x 1 0 -19 J
=
ë 1m In 1913, Niels Bohr proposed a model for electron distributions
532 nm x
109 nm that was a combination of classical and the new emerging quantum
theories.
hí o = 6.626 x 10 - 34 J ⋅ s x 3.66x10 14 s-1 = 2.43 x 1 0 -19 J 1. Electrons move in circular orbits about the nucleus.
1 2. These “orbits” are fixed or discrete in terms of allowed
m e v 2 = 1.31 x 1 0 -19 J energies governed by states of angular momentum.
2
3. Electrons can only pass between these allowed levels and
nowhere in between.
1.31 x 1 0 -19 J m
v= 2x = 5.36 × 105
- 31
9.11 x 10 kg s Conclusion: The energy levels of the electrons are quantized!
This explains the observance of line spectra in atom emission.

To explain the spectral line puzzle, Bohr came up with a radical

model of the atom, whichZ had electrons orbiting around a nucleus.
i
Because of thesep "signature colors” or emission lines, Bohr stated
p to exist in discrete orbits or “quantized” levels
that electrons had
y
and that the spectral lines occurred when the electron jumped
,
between the allowed levels.
e
Each level is designated by a “Quantum Number”, n
h
n = 1,2,3,4…. infinity

the radius of each orbit is given by:

rn = n2ao The Bohr radius ao = 0.53 Å or 53 pm

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 Atomic structure
The energy of each level is given by:

- Z2 R H
En =
n2

Where RH = 2.179 x 10 -18 J

The Bohr Model:

rn = n2ao

n = 1, 2, 3, 4…

The Energy Levels:

- Z2 R H
En =
n2

The Lowest energy level corresponds to n = 1

Where, n = 1 “Ground State”

n=2 “1st excited state”
n=3 “2nd excited state”
n = n-1 “nth excited state”

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 Atomic structure
Absorption and Emission - Z2R H
En = for Z =1
n2
When an electron jumps form a lower state to a higher state,
Energy (light) is absorbed.
-RH -RH
ÄE = E fin - E in = - 2 = E photon
When an electron jumps form a higher state to a lower state, n 2fin n in
Energy is (light) emitted

Emission of Light:  1 1  h ⋅c
ÄE = R H ×  2 − 2  = h ⋅ν =
 n in n fin  λ
Electrons move from
a higher level (state)
to a lower level (state)
1 RH  1 1 
= ×  2 − 2 
λ h ⋅ c  n in n fin 

Absorption of Light: A negative signs indicates emission, positive absorption.

The Wave-like Nature of a Particle
Electrons move from
a lower level (state) to
a higher level (state)

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 Atomic structure
The Wave Particle Duality: Heisenberg Uncertainty Principle:

Louis de Broglie in response to Planck & Einstein’s assertion that The more precisely the position is determined, the less precisely
light was “particle-like” (photon) stated that small particles moving the momentum is known in this instant, and vice versa.
fast could exhibit a characteristic wavelength.
∆p ∆x > h / 4π
E = mc 2

∆p = uncertainty in momentum
(velocity)
hυ = mc 2 ∆x = uncertainty in position

hυ
= mc = p (momentum) Classically, i.e., in our macroscopic world, I can measure these
c
two quantities to infinite precision (more or less). There is really
no question where something is and what its momentum is.
υ 1
since =
c ë
In the Quantum Mechanical world, the idea that we can measure
h h h things exactly breaks down, i.e. there is a limit to the precision.
= p or λ = = u = velocity
λ p m⋅ u This uncertainty leads to many strange things.
What is the wavelength associated with an 80g tennis ball (d = 8 For example, in a Quantum Mechanical world, I cannot
cm) moving at 115 miles per hour? predict where a particle will be with 100 % certainty. I can
Compare that to an electron moving at 1/100 the speed of light. only speak in terms of probabilities.

h λ A consequence of the Quantum Mechanical nature of the world is

λ= λ (tennis ball) = 2 x 10 –34 m × 100 = 2 x 10-31 %
p d that particles can appear in places where they have no right to be
(from an ordinary, common sense [classical] point of view)!
λ
λ (electron) = 2 x 10 – 10 m × 100 = 70000 %The
d
electron looks like a wave!

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 Atomic structure
The results state that there is a “probability” of finding the particle Quantum numbers and Electron Orbitals
in space at position “x” with an uncertainty of ∆x.
Quantum Numbers are terms that were developed to aid in
The location of a particle is given by a localized increase in the describing electron behavior according to the Schrödinger
amplitude of the wave at position x. equation.
Principal Quantum Number “n”

Probability Distributions: n = 1, 2, 3, 4…up to infinity

The mental picture of an electron Azimuthal or Angular Quantum Number “l”

corresponds to a wave superimposed
upon the radial trajectory of a particle l = 0, 1, 2, 3…up to a maximum of “n – 1”
orbiting the nucleus.
Magnetic Quantum Number “ml”

ml may take on the value an integer from

The position of an electron is best -l to +l
described by the image of a dart
board: As the Schrödinger Wave Spin Quantum Number “ms ”
Equation is solved time and time
ms ± 1/2
again, the position of an electron is
found such that each “hit” builds up a
pattern. The Quantum numbers give information about the location of an
The build up of “hits” yields the probability in 3-dimensons for electron, like an address.
The principal quantum number indicates the “state” where the
the likelihood of finding and electron about the nucleus.
electron is located, the angular momentum quantum number
• It is these probability functions that give rise to the familiar
indicates the town, the magnetic QN is the street address and the
hydrogen-like orbitals that electrons occupy.
spin quantum number corresponds to the right or left side of a
duplex.

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 Atomic structure
for l=0 ml = 0 (no orientation)

for l=1 ml = -1 0 +1
px py pz

for l=2
Each n-level defines a principle
energy level or shell. ml = -2 -1 0 +1 +2
n = 1, 2, 3… and

Z2R H
En = − 2
n

Z = atomic number of the

nucleus and R H = Rydberg
constant.

Each “l” within an “n-level” represents a subshell.

l=0 “s” subshell Each orbital can hold
l= 1 “p” subshell 2 electrons,
l=2 “d” subshell one designated by ms
l=3 “f” subshell =+½
and one by ms = − ½
Each “l” subshell is divided into ml orbitals, where ml designates
the spatial orientation of each orbital. (Cartesian coordinates, x, y
& z)

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Atomic structure

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 Atomic structure
Electron Configurations: Multi-electron atoms This increase in the ability to penetrate magnifies the ability to
screen.

The ideas
presented thus s-orbitals > p or d-orbitals
far have
focused on the Increasing Screening
H-atom, a one-
electron
system. The effect of Shielding:

What happens In a hydrogen atom,

when there are the orbitals are
two or more arranged as a function
electrons in an of “n” only.
atom?
For each value of n,
The diagram the l-sub shells are
to the right degenerate (of the
explains: same energy).

Shielding brought
• The innermost electrons screen or “shield” the nucleus upon by the presence
from the view of the outer electrons. of more than one
• The outermost electrons in effect see a charge that is less electron causes the
that the actual charge on the nucleus, Z. orbital energies to
split.
Shielding of Electrons:

The further out an electron exists from the nucleus, the greater the
effect of shielding. (There are more electrons to screen the nucleus
charge)

Since the s-orbitals have no nodal properties at the nucleus, they

can penetrate more effectively.

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 Atomic structure
Electron Configuration of Many Electron Elements

The electrons of a many-electron atom occupy the orbitals in

accordance with a series of rules.

The Pauli Exclusion Principle:

Only two electrons with opposite spin can occupy an

atomic orbital.

Stated another way, no two electrons have the same 4 quantum

numbers n, l, ml, ms.

In applying this rule, you should realize that an atomic orbital is an

energy state.

Hund's rule:
The result of shielding causes the
orbitals to arrange in terms of Electrons prefer parallel spins in separate orbitals of sub
increasing n + l shells.
3 Electrons will fill across a set of degenerate orbitals until forced to
This results in the 4s-orbital having 4 pair with opposite spins.
a lower energy that that of the
3d-orbital. 3
The Aufbau (Building up) Principle:
n = l = 4 + 0 vs. 3 + 2
2 Electrons fill from the lowest energy states (orbitals) up.

E=n+l The Aufbau procedure (filling order of atomic orbitals) is used to

work out the electron configurations of all atoms.

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 Atomic structure

Electron Configurations of the 1st and 2nd Period:

H = 1s1 C = 1s2 2s2 2p 2

He = 1s2 N = 1s2 2s 2 2p3

Li = 1s2 2s 1 O = 1s2 2s 2 2p4

Be = 1s2 2s2 F = 1s2 2s2 2p 5

B Z = 5 5 electrons B = 1s2 2s2 2p 1 Ne = 1s2 2s2 2p 6

↑↓ ↑↓ ↑

1s 2s 2p

1s22s22p 1

O Z = 8 8 electrons

↑↓ ↑↓ ↑↓ ↑ ↑

1s22s22p 4

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 Atomic structure
Valence Electon Blocks:
Electron Configurations continued:

Electrons in the outermost shell are called valence electrons.

• It is the valence electrons determine an atom’s chemical properties.
• Electrons in the inner shells are inner electrons or core electrons.
• Regions in periodic table are designated as the s-block, p-block, d-block and the f-block.

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 Atomic structure

Core Notation:

[Nobel Gas]
nd(n+1)s

Some
anomolies in
filling are seen
in the d-
elements

For d4 and d 9
elements, an s-
electron can
jump over to
create a ½
filled (d5)or What is the electron
completely configuration of the element
filled (d10) d- as shown on the right?
orbital.
Which electrons are the
This lowers the valence electrons and which
overall energy are the core electrons?
of the atom.

Answers:

1s22s22p 63s23p 6 P (phosphorous)

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 Atomic structure
The formation of the phosphide ion:

P (1s22s22p63s 33p3) P3- (1s22s 22p63s 33p 6) = [Ar]

Core electrons Valence electrons

All group 5 (15) anions (-3) will have the electron configuration
of the next Nobles gas.
Electron Configurations of ions:
Electron configurations of Transition Metal Ions:
When an atom gains or loses electrons it becomes an ion. The charge states on most transition metals cannot be equated to
the electron configurations of the Noble gases. You will see why in
Loss of electrons: Cation Gain of electrons: chem. 2C (ch. 24 and 25)
Anion
The electron configurations of transitions metal cations must be
(+) determined from the charge state.

(-) Fe3+… 3 electrons lost Ni2+… 2 electrons lost and so on.

Atoms of group 1, 2 and the non-metals will lose or gain electrons • When transition metals ionize, they lose the s-electrons
to attain the electron configuration of a Nobel gas (ns2np6). first.
• This may seem odd as it is opposite to the filling order.
Example: Sodium forming sodium • From a stability argument, the removal of the s-electrons
ion: first results in lower energy configuration when we take
Na Na+ into account ionization energies of s vs. p and d electrons.
[Ne]

3d1 4s2
Examples:
1s22s2sp63s 1 1s22s2sp6

All group 1 cations (+1) will have the electron configuration of the
previous Noble gas.
Sc3+:
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 Atomic structure

Cr3+: [Ar] 3d 3

Electron Configurations:
Excited States

Which of the electron

configurations to the right
corresponds to phosphorous?

Answer: c
The rest are excited states of
phosphorous.

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