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Quantum Mechanics and the Atom

Quantum numbers

• Plot of Y 2 represents an orbital.

• The electrons in each orbital have very specific
energies.
• Each of these orbitals can be described by a series
of numbers (quantum numbers) which describe
various properties of the orbital.

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 Quantum Mechanics and the Atom
Quantum numbers

• Principle quantum number (n) – overall size and

energy of the orbital
• Angular momentum quantum number (l) – shape of
orbital
• Magnetic quantum number (ml) – orientation of
orbital
• Spin quantum number (ms)– direction of spin of the
electron

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 Principal Quantum Number, n
• Characterizes the energy of the electron in a particular
orbital.
• n can be any integer  1.
• The larger the value of n, the more energy the orbital has.
• Energies are defined as being negative. The energy of the electron in a hydrogen
atom has a negative sign for all possible orbits. ... This negative sign means that the energy of the electron in the atom is lower than the
energy of a free electron at rest.

• The larger the value of n, the larger the orbital.

• For the hydrogen atom, the energy of an electron in an
orbital with quantum number n is given by the equation:

The constant, 2.18 ×10- 18 J, is known as the Rydberg constant( RH)

 Principle Quantum Number (n)
• Integer that determines the overall size and energy of the
orbital
• n = 1, 2, 3, ….
• The energy of the orbital is given by

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 Energy Transitions in Hydrogen
• The energy of a photon released is equal to the
difference in energy between the two levels the
electron is jumping between.
• It can be calculated by subtracting the energy of
the initial state from the energy of the final state.

DEelectron = Efinal state − Einitial state

Calculate the wavelength of light emitted when the
hydrogen electron transitions from n = 6 to n = 5
Given: ni = 6, nf = 5
Find: , m

hc
DEatom = -Ephoton 
E

18 1 1 
DE atom  2.18 10 J 2  2   2.6644 10 20 J
5 6 

Ephoton = -(-2.6644 x 10-20 J) = 2.6644 x 10-20 J

hc 6.626 10
 

34
3.00 10 
Js
 7.46 10
8 m
6
2.6644 10 
s
-20
m
E J
Calculate the wavelength of light emitted when the hydrogen
electron transitions from n = 2 to n = 1
Given: ni = 2, nf = 1
Find: , m

hc

E

1 1 
DE atom  2.18 10 18 J 2  2   1.64 10 18 J
1 2 
Ephoton = -(-1.64 x 10-18 J) = 1.64 x 10-18 J

hc 6.626 10
 
3.00 10 
34
Js
 1.2110
8 m
7
1.64 10 
s
-18
m
E J
Quantum Mechanics and the Atom
Exercise

What color of light is emitted when an excited

electron in the hydrogen atom falls from:
a) n = 5 to n = 2
b) n = 4 to n = 2
c) n = 3 to n = 2

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 Angular Momentum Quantum Number, l

• The angular momentum quantum number

determines the shape of the orbital.
• l can have integer values from 0 to (n – 1).
• Each value of l is called by a particular letter that
designates the shape of the orbital.

s orbitals are spherical.

p orbitals are like two balloons tied at the knots.
d orbitals are mainly like four balloons tied at
the knots.
f orbitals are mainly like eight balloons tied at the
knots.
 Magnetic Quantum Number, ml
• The magnetic quantum number is an integer that
specifies the orientation of the orbital.
The direction in space the orbital is aligned relative to
the other orbitals

• ml values are integers from −l to +l

Including zero
Gives the number of orbitals of a particular shape
When l = 2, the values of ml are −2, −1, 0, +1, +2,
which means there are five orbitals with l = 2.
 Spin Quantum Number ms

• Spin quantum number

• Specifies the direction of spin of the electron
• Indicated by the letter ms
• Electrons either spin up + ½ or down – ½

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 Summary of Quantum Number

• Principle (n) 1, 2, etc.

• Shape (l) 0 to n minus 1

• Orientation (ml) – l to + l

• Electron spin + ½ (up) – ½ (down)

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 Describing an Orbital
• Each set of n, l, and ml describes one orbital.

• Orbitals with the same value of n are in the

same principal energy level.
Also called the principal shell

• Orbitals with the same values of n and l are

said to be in the same sublevel.
 Also called a subshell
Energy Levels and Sublevels
The n = 2 principal energy level
contains two sublevels:

a. The l = 0: 2s sublevel with

one orbital with ml = 0

b. The l = 1: 2p sublevel with

three p orbitals with
ml = -1, 0, +1
 Quantum Numbers
Which of the following are possible sets of
quantum numbers?
a) 1, 1, 0, +1/2 l value not possible
b) 2, 0, 0, +1/2 possible
c) 3, 2, 2, 1/2 possible
 Quantum Mechanical Explanation of Atomic Spectra

• When atom absorbs energy electron is excited to higher energy

orbital. But this atoms is unstable
• Electron quickly falls back (relaxes) to a lower energy orbital –
releases a photon of light. Energy of that photon is exactly equal
to the difference in energy between the two levels

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Predicting the Spectrum of Hydrogen
• The wavelengths of lines in the emission spectrum
of hydrogen can be predicted by calculating the
difference in energy between any two states.

• For an electron in energy state n, there are

(n – 1) energy states it can transition to. Therefore,
it can generate (n – 1) lines.

• Both the Bohr and quantum mechanical models can

predict these lines very accurately for a 1-electron
system.
Hydrogen Energy Transitions and Radiation
Probability and Radial Distribution Functions
• y 2 is the probability density.
 The probability of finding an electron at a particular point
in space
 For s orbital maximum at the nucleus
 Decreases as you move away from the nucleus

• The radial distribution function represents the total

probability at a certain distance from the nucleus.
 Maximum at most probable radius

• Nodes in the functions are where the probability drops to

0.
 Probability Density Function
The probability density function represents the total
probability of finding an electron at a particular point in space.

Note that its value is greatest nearest the nucleus, but rapidly
decreases thereafter. Note also that it never goes to zero, only
to a very small value.
 Radial Distribution Function
The radial distribution function
represents the total probability of
finding an electron within a thin
spherical shell at a distance r from
the nucleus.
The probability at a point
decreases with increasing
distance from the nucleus, but the
volume of the spherical shell
increases.
The net result is a plot that
indicates the most probable
distance of the electron in a 1s
orbital of H is 52.9 pm.
the probability of finding the electron somewhere on a given radius circle is found by
multiplying the probability density by 4πr2 . This yields the curve you have probably
as the radial probability, that is shown on the right side of the above diagram. The
peak of the radial probability for principal quantum number n=1 corresponds to the
Bohr radius.
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For the hydrogen 1s orbital, the maximum radial
probability occurs at a distance of 52.9 pm from the
nucleus. This is exactly the radius of the innermost orbit in
the Bohr model.

Note that in Bohr’s model the electron is assumed to have a

circular path and so is always found at this distance.

In the quantum mechanical model, the specific electron

motions are unknown, and this is the most probable (the
sphere that encloses 90% of the total electron probability)
distance at which the electron is found

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 Nodes
The 1s radial distribution function has no nodes but the
higher s orbitals do. The number of nodes is related to the
principal quantum number, n. In general, the ns orbital
have (n - 1) radial nodes. Therefore, the 1s-orbital has (1 -
1) = 0 radial nodes, as shown in the above plot. Radial
nodes become evident in higher s-orbitals ( 2s, 3s, 4s, 5s,
6s, and 7s).

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2s and 3s
 The Shapes of Atomic Orbitals
• The l quantum number primarily determines the
shape of the orbital.
• l can have integer values from 0 to (n – 1).
• Each value of l is called by a particular letter
that designates the shape of the orbital.
s orbitals are spherical.
p orbitals are like two balloons tied at the knots.
d orbitals are mainly like four balloons tied at the
knots.
f orbitals are mainly like eight balloons tied at the
knots.
 l = 0, the s Orbital

• Each principal energy level

has one s orbital
• Lowest energy orbital in a
principal energy state
• Spherical
• Number of nodes = (n – 1)

Nodes= zero
 l = 1, p orbitals

• Each principal energy state above n = 1 has three p

orbitals.
 ml = −1, 0, +1
• Each of the three orbitals points along a different axis
 px, py, pz
• The second lowest energy orbitals in a principal energy
state
• Two-lobed
• One node at the nucleus; total of n nodes
p Orbitals
 l = 2, d Orbitals
• Each principal energy state above n = 2 has five
d orbitals.
ml = −2, − 1, 0, +1, +2
• Four of the five orbitals are aligned in a different plane.
The fifth is aligned with the z axis, dz squared.
dxy, dyz, dxz, dx squared – y squared
• The third lowest energy orbitals in a principal energy level
• Mainly four-lobed
• Planar nodes
d Orbitals
 l = 3, f Orbitals
• Each principal energy state above n = 3 has seven d
orbitals.
 ml = −3, −2, −1, 0, +1, +2, +3
• The fourth lowest energy orbitals in a principal
energy state
• Mainly eight-lobed
 Some two-lobed with a toroid
• Planar nodes
f Orbitals
Why Are Atoms Spherical?
3D animated version of S and P orbitals
https://www.youtube.com/watch?v=z8VYWR7S98o