The Quantum Mechanical Model of the Atom

In the 1920’s Erwin Schrödinger applied the principles of wave mechanics to atoms and
developed the Quantum Mechanical Model of the Atom. • This theory builds on Bohr’s
idea of quantized energy levels (orbits) and adds additional requirements for electron
location and energy.

Important Principles
de Broglie (1925) proposed that not only does light have the dual properties of waves
and particles, but also particles of matter have properties of waves. The wavelength of
those particle waves is given by λ = h/ mv, where m and v are the mass and velocity of
the particle.
Planck’s constant, h, is so small that the wavelengths are in an observable range only for
particles of atomic or subatomic mass.
He studied the wave-particle duality of light as suggested by Albert Einstein and
extended this idea to include other objects such as the electron.
The energy of an object (E) in motion is equal to its mass (m) times the square of its
speed (c):
E = mc2

The energy of a wave (E) is proportional to its frequency (v) which is proportional to its
speed (s) and inversely proportional to its wavelength ( ) where h is Planck's
constant:
E = hv = hc/λ

If an object acts as both a particle in motion and a wave, then the two equations can be
combined:
mc2 = hc/λ
Cancelling like terms and rearranging the equation to solve for the wavelength results
in the following:
λ = h/mc

By defnition, momentum (p) of an object is equal to the product of its mass (m) times its
speed (c), so p can be substituted for ms to get the de Broglie equation.
de Broglie equation - The wavelength ( ) of an object in motion is inversely
proportional to its momentum (p) where h is Planck's constant (6.626 x 10-34 J-
s):

ie λ = h/mc
With this equation, if the mass of an object is too large (as it is with most objects), the
wavelength would be negligible. Very small particles such as electrons, however, are
small enough to exhibit the properties of both waves and particles.
Since electrons act as waves as well as particles, they cannot be restricted to circular
orbits, but rather must exist in three-dimensional space. Atoms or ions with a single
electron are simple enough to be explained using the Bohr model which assumes that
electrons travel in circular orbits around the nucleus. An atom or ion with any more
electrons, however, is too complex to be explained by the Bohr model.

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  Heisenberg Uncertainty Principle - It is impossible to determine
the position (x) and the momentum (mv) of a particle simultaneously with
certainty.
In the Bohr model, it is assumed that there are fixed angular momentums for each
quantized orbital.

 Erwin Schrödinger developed a model of the atom which accounted for the
wave and particle-like behavior of electrons. Instead of restricting electrons to
limited circular orbits, he developed a new idea of orbitals:
Orbitals - regions in space where electrons are most likely to be found. An orbital is a
region in space around a nucleus where there is a high probability of finding the
electron.
This no longer violated the Heisenberg Uncertainty Principle as the Bohr model did
since the exact location of an electron at any moment in time is not known.
 Bohr's one-dimensional model required only one coordinate to describe the size
of the circular orbit in which an electron could be found. Schrödinger's three-
dimensional model requires three coordinates, or quantum numbers, which
describe the orbitals where electrons can be found.

Quantum Numbers
1) Principal quantum number (n) - describes the SIZE of the orbital. Since the
distance from of an electron from the nucleus is directly proportional to the
energy of the electron (as described in the Bohr model), the principal quantum
number is also a measure of energy of the orbital. The principal quantum
number denotes the energy level of electrons. The larger the principal quantum
number is, the larger the energy. • The orbital size depends on n. This means that
the larger the n value, the larger the orbital. Orbitals with the same n belong to
the same shell.
2) Angular quantum number (l) - describes the SHAPE of the orbital.
o The s orbitals are spherical (l = 0).
o The p orbitals are polar (l = 1).
o The d orbitals are clover-leaf shaped (l = 2).

3) Magnetic quantum number (m) - describes an orbital's ORIENTATION in

space.
o For s orbitals (l = 0), there is only one orientation possible, so m must
equal 0.

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 o For p orbitals (l = 1), there are three possible orientations, so m can be -1,
0, or 1.
 (see picture below)

o For d orbitals (l = 2), there are five possible orientations, so m can be -2, -
1, 0, 1, or 2.

4) Spin quantum number (ms) - describes the SPIN or direction (clockwise or

counter-clockwise) in which an electron spins. If there are two electrons in any
one orbital, they will have opposite spins, that is, one will have a + spin and the
other will have a - spin. The maximum number of electron in any one orbital is
two.

Shells and Subshells

 Shell - A group of orbitals with the same principal quantum number
e.g. The 2s and 2p orbitals.
 Subshell - A group of orbitals with the same angular quantum number

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 e.g. The three 2p orbitals: 2px, 2py, and 2pz

Rules for Allowable Combinations of Quantum Numbers

 The three quantum numbers (n, l, and m) that describe an orbital must be
integers.
 "n" cannot be zero. "n" = 1, 2, 3, 4...
 "l" can be any integer between zero and (n-1).
e.g. If n = 4, l can be 0, 1, 2, or 3.
 "m" can be any integer between -l and +l.
e.g. If l = 2, m can be -2, -1, 0, 1, or 2.
"s" is arbitrarily assigned as + or - , but for any one subshell (n, l, m combination),
there can only be one of each.

Graphical Representation of Allowable Combinations of Quantum Numbers

Shell Subshell Subshell Orientation Number of

n l Notation ml Orbitals
1 0 1s 0 1
2 0 2s 0 1
1 2p -1 0 +1 3
3 0 3s 0 1
1 3p -1 0 +1 3
2 3d -2 -1 0 +1 +2 5
4 0 4s 0 1
1 4p -1 0 +1 3
2 4d -2 -1 0 +1 +2 5
3 4f -3 -2 -1 0 +1 +2 +3 7

Example Quantum Number Problem

List the quantum numbers of all the electrons in a neon atom.
1s {
100 2 1 -1
2s {
200 210

2p 211

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Electron Configurations and orbital diagram

Electron Configuration - Describes the distribution of electrons in atomic orbitals

according to specific rules.
Electron Diagram - Illustrates the distribution of electrons in atomic orbitals according
to specific rules.

1) Aufbau Principle ( Building up principle)

Electrons are added one at a time, starting with the lowest energy orbital until all the
electrons have been accounted for.

Relative Energies of Atomic Orbitals

Many of an element’s chemical properties depend on its electron configuration. The

electron configuration of an atom is a shorthand method of writing the location of
electrons by sublevel.

The principal energy level (n) is written first, followed by the letter designation of the
sublevel (l) then a superscript with the number of electrons in the sublevel.
– Electrons are arranged about the nucleus in a regular manner.
– The first electrons fill the energy sublevels closest to the nucleus.
– Electrons continue filling each sublevel until it is full and start filling the next closest
sublevel.

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Order: 1s < 2s < 2p <3s < 3p<4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f <5d...

2) Pauli Exclusion Principle

 An orbital can hold a maximum of 2 electrons.
 2 electrons in the same orbital must have opposite spins.
 An electron is "paired" if it is sharing an orbital with another electron with an
opposite spin.
 An electron is "unpaired" if it is alone in an orbital
A H atom has one electron which is unpaired in the lowest energy orbital, 1s.

H: 1s1
A He atom has two electrons; the second one fills the 1s orbital with a spin opposite
that of the first electron. These two electrons are now paired.

He: 1s2
A Li atom has 3 electrons; the third one is added to the next lowest energy orbital, 2s
and is unpaired.

Li: 1s22s1
A Be atom has 4 electrons; the fourth one is fills the 2s orbital with a spin opposite that
of the first electron in the orbital. These two electrons are now paired.

Be: 1s22s2
A B atom has 5 electrons; the fifth one is added unpaired to the next lowest energy
orbital, 2p.

B: 1s22s22p1

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 The p subshells have 3 orbitals, each which can hold two electrons. Orbitals within the
same subshell (e.g. 2px, 2py, and 2pz) have identical sizes and shapes, and only their
orientation differs. Therefore, these orbitals are called degenerate orbitals because
they have the same energy.

3) Hund's Rule
Electrons are added to degenerate, equal energy, orbitals so that a maximum number
of unpaired electrons results.
O: 1s22s22p4

B: 1s22s22p1

F: 1s22s22p5

C: 1s22s22p2

Ne: 1s22s22p6

N: 1s22s22p3

An atom is diamagnetic if all of its electrons are paired. e.g. Of the atoms listed directly
above, only Ne is diamagnetic. Atoms ending with xs2, xp6, xd10, and xf14 are
diamagnetic.
An atom is paramagnetic if it has one or more unpaired electrons
e.g. B, C, N, O, and F above are all paramagnetic because they all have at least one
unpaired electron.
Electron configurations are often abbreviated by naming the last element with a filled
shell (e.g. He and Ne) in brackets and listing only the orbitals after the filled shell. This
outermost shell is called the valence shell and the electron in the valence shell are
called valence electrons.

Li: 1s22s1 shorthand Li: [He] 2s1

Na: 1s22s22p63s1 shorthand Na: [Ne] 3s1

Atomic Symbol Electron Electron

Number Configuration Diagram
1 H 1s1

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2 He 1s2

3 Li [He] 2s1

4 Be [He] 2s2

5 B [He] 2s22p1

6 C [He] 2s22p2

7 N [He] 2s22p3

8 O [He] 2s22p4

9 F [He] 2s22p5

10 Ne [He] 2s22p6

11 Na [Ne] 3s1

12 Mg [Ne] 3s2

13 Al [Ne] 3s23p1

14 Si [Ne] 3s23p2

15 P [Ne] 3s23p3

16 S [Ne] 3s23p4

17 Cl [Ne] 3s23p5

18 Ar [Ne] 3s23p6

19 K [Ar] 4s1

20 Ca [Ar] 4s2

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21 Sc [Ar] 4s23d1

22 Ti [Ar] 4s23d2

23 V [Ar] 4s23d3

24 Cr [Ar] 4s13d5

25 Mn [Ar] 4s23d5

26 Fe [Ar] 4s23d6

27 Co [Ar] 4s23d7

28 Ni [Ar] 4s23d8

29 Cu [Ar] 4s13d10

30 Zn [Ar] 4s23d10

31 Ga [Ar] 4s23d104p1

32 Ge [Ar] 4s23d104p2

33 As [Ar] 4s23d104p3

34 Se [Ar] 4s23d104p4

35 Br [Ar] 4s23d104p5

36 Kr [Ar] 4s23d104p6

Exceptions to the predicted electron configurations

Two elements of the first 40 elements have electron configurations different from what
would be normally predicted.

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Predicted: Cr: [Ar] 4s23d4

Actual: Cr: [Ar] 4s13d5

Predicted: Cu: [Ar] 4s23d9

Actual: Cu: [Ar] 4s13d10

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