LESSON 20:

ELECTRONIC
STRUCTURE OF THE
ATOM
By: Michael R. Maglaque
General Chemistry 1
Facilitator
I. HEISENBERG’S UNCERTAINTY
PRINCIPLE
■ With the discovery that particles like electrons are wavelike
(shown by De Broglie, Davisson and Germer, and Thomson),
how can the ‘position’ of a wave be specified? How can the
precise location of a wave be defined when a wave extends in
space?
■ Werner Heisenberg, a German physicist, formulated what is
now known as Heisenberg’s Uncertainty Principle which
states that “the position of a particle and its momentum cannot
be simultaneously measured with arbitrarily high precision.”
In other words, it is not possible to measure the exact position
and the exact momentum of a particle at the same time.
Mathematically, this is stated as
where “x” is the uncertainty in position, “p” is the uncertainty
in momentum, and “h” is Planck’s constant.
■According to the Bohr model, the
electron goes around the nucleus in
well-defined orbits, the radius of
which can be determined.
■How can you relate the Bohr
model to Heisenberg’s
Uncertainty Principle?
■ The Bohr model violates Heisenberg’s Uncertainty
Principle. Electrons do not go around the nucleus in
well-defined orbits. Otherwise, we will be able to
determine the exact position and momentum of the
electron in the atom at the same time. A better model is
needed to fully describe the atom.
An electron is travelling at a speed of 2.05 x
106 m/s. Assuming that the precision
(uncertainty) of this value is 1.5%, with what
precision can the position of the electron be
measured?
■This value shows that the electron’s
position is about 10 atomic diameters.
Given the uncertainty of the speed,
there is no way to pin down the
electron’s position with any greater
accuracy.
■Why is the uncertainty
principle not significant when
applied to large objects such as
a transportation vehicle?
II. THE SCHRODINGER EQUATION
■ While the Bohr model of the atom could explain the emission spectrum of
hydrogen, it could not account for many observations and could not
provide a complete description of the electronic behavior in atoms.
■ In 1926, Erwin Schrodinger, an Austrian physicist, formulated a
mathematical equation that describes the behavior and energies of
submicroscopic particles. The Schrodinger equation incorporates particle
behavior and wave behavior, treating the electron as a standing wave. The
solution to the Schrodinger equation is a wave function called ψ (psi). The
wave functions are also called atomic orbitals (as distinguished from the
Bohr orbits). Aside from the wave functions, energies are also obtained
from solving the equation.
■ The wave function itself has no physical meaning. However, the
probability of finding the electron in a particular volume element
in space is proportional to ψ2. In wave theory, the intensity of
light is proportional to the square of the amplitude of the wave
or ψ2. Similarly, the most likely place to find the particle is
where the value of ψ2 is greatest.
■ The Schrodinger equation began a new field in physics and
chemistry referred to as quantum mechanics or wave
mechanics. The Schrodinger equation can be solved exactly for
the hydrogen atom but not for atoms with more than one
electron. For many-electron atoms, approximation methods are
used to solve the Schrodinger equation.
The Schrodinger equation for the hydrogen
atom looks like this:
■The solution of the Schrodinger equation
involves advance calculus and differential
equations. The lesson will only deal with
the interpretation of the solution.
 III. THE QUANTUM MECHANICAL
DESCRIPTION OF THE HYDROGEN ATOM
■ It is not possible to pinpoint the exact location of the
electron in an atom but ψ2 gives the region where it
can most probably be found. The electron density
gives the probability that the electron will be found in
a particular region of an atom. Figure (a) is a
representation of the electron density distribution
around the nucleus in the hydrogen atom. The darker
the shade, the higher the probability of finding the
electron in that region.
■ In this case, the probability distribution is
spherical. The probability can also be plotted versus
the distance from the nucleus as shown in Figure
(b). It can be seen that there is a probability of
finding the electron even very far from the nucleus,
although this probability is small. The closer to the
nucleus, the higher the probability.
 (a) (b)

a) and (b) Probability of Finding the Electron in the Ground State of the Hydrogen Atom at Different Points in
Space, “Atomic Orbitals and Their Energies”, section 6.5 from the book Principles of General Chemistry (v. 1.0),
Retrieved from http://2012books.lardbucket.org/books/ principles-of-general-chemistry-v1.0/s10-05- atomic-
orbitals-and-their-ener.html (2 Nov. 2016), Creative Commons by-nc-sa 3.0 license.
■ As mentioned earlier, ψ is the solution to the
Schrodinger equation. It is also referred to as an atomic
orbital. When we say that the electron is in an atomic
orbital, we mean that it is described by a wave function,
ψ, and that the probability of locating the electron is
given by the square of the wave function associated with
that orbital. Therefore, the atomic orbital has a
characteristic energy as well as a characteristic
electron density distribution. This electron density
distribution in three-dimensions gives the shape of the
atomic orbital.
IV. THE QUANTUM NUMBERS
■ In the mathematical solution of the Schrodinger
equation, three quantum numbers are obtained. These
are:
1. principal quantum number (n),
They describe the
2. angular quantum number, (ℓ) atomic orbitals.
3. magnetic quantum number (ml).
4. spin quantum number (ms)-completes the
description of the electrons in the atoms.
 1. The Principal Quantum Number (n)
a. Determines the energy of an orbital
b. Determines the orbital size
c. It is related to the average distance of the electron
from the nucleus in a particular orbital; the larger the n
value, the farther the average distance of the electron from
the nucleus
d. Can have the values: n = 1, 2, 3, …
e. Orbitals with the same n are said to be in the same shell.
2. The Angular Momentum Quantum Number (ℓ)

a. Describes the “shape” of the orbitals

b. Can have the following values: ℓ = 0, 1, 2, up to n-1.
■The s, p, d, f designations of the
orbitals refer to sharp, principal,
diffuse, and fundamental lines in
emission spectra.
3. Magnetic Quantum Number (ml)
a. Describes the orientation of the
orbital in space
b. Can have the values:
- ℓ, (-ℓ + 1), … 0, … (+ ℓ -1), + ℓ
4.Electron Spin Quantum Number (ms)
a. The first three quantum numbers describe the energy, shape and
orientation of orbitals. The 4th quantum number refers to two
different spin orientations of electrons in a specified orbital.
b. When lines of the hydrogen spectrum are examined at very high
resolution, they are found to be closely spaced doublets and called
as the Zeeman effect. This splitting is called fine structure, and
was one of the first experimental evidences for electron spin. The
direct observation of the electron's intrinsic angular momentum
was achieved in the Stern–Gerlach experiment.
4.Electron Spin Quantum Number (ms) Continuation….

c. Uhlenbeck, Goudsmit, and Kronig (1925) introduced the idea of the self-
rotation of the electron. The spin orientations are called "spin-up" or "spin-
down" and is assigned the number ms = ½ ms = -½, respectively.
d. The spin property of an electron would give rise to magnetic moment, which
was a requisite for the fourth quantum number. The electrons are paired such
that one spins upward and one downward, neutralizing the effect of their spin on
the action of the atom as a whole. But in the valence shell of atoms where there is
a single electron whose spin remains unbalanced, the unbalanced spin creates spin
magnetic moment, making the electron act like a very small magnet. As the atoms
pass through the in-homogeneous magnetic field, the force moment in the
magnetic field influences.
Quantum numbers must be in order…
■ The four quantum numbers compose the
numbers that describe the electron in an atom.
The quantum numbers shall be in the order:
energy level (n), sub-level or orbital type (ℓ),
the orientation of the orbital specified in ℓ (mℓ),
and the orientation of the spin of the electron
(ms).
It is written in the order (n, ℓ, mℓ, ms ).
For example:

1. An electron is found in the first energy level. What is the

allowed set of quantum numbers for this electron?
a. The energy level, n = 1.
b. The orbital type is only s, its designation is 0, thus, ℓ = 0
c. From ℓ, the orbital type is s. There is only one orientation
of an s orbital, designated as 0, thus, mℓ = 0.m
d. An electron in the 1s orbital can have an up-spin or a
down-spin. Therefore, ms could be +1/2 or -1/2.
■So the allowed set of quantum numbers for 1s electron are:
(1,0,0,1/2) and (1,0,0,-1/2)
How does (1,0,0,1/2) differ from (1,0,0,-1/2)?
Answer…
■The first set corresponds to the
electron with spin up and the
second set refers to the electron
with spin down.
V. THE QUANTUM NUMBERS AND THE
CORRESPONDING ATOMIC ORBITALS
Exercises
A.
1. What is the total number of orbitals associated with the
principal quantum number n=1?
2. What is the total number of orbitals associated with the
principal quantum number n=2?
3. What is the total number of orbitals associated with the
principal quantum number n=3?
4. We can therefore say that the total number of orbitals
associated with a given principal quantum number n is n2.
B. List the values of n, ℓ , mℓ for an orbital in the 4d subshell.
Exercises:
1. What is the total number of orbitals associated with the principal quantum
number n=1?
Answer: 1
2. What is the total number of orbitals associated with the principal quantum
number n=2?
Answer: 4
3. What is the total number of orbitals associated with the principal quantum
number n=3?
Answer: 9
We can therefore say that the total number of orbitals associated with a
given principal quantum number n is n2.
B. List the values of n, ℓ , mℓ for an orbital in the 4d subshell.
Answer: n=4; ℓ =2; ml can have the values of -2, -1, 0, 1, 2
 The Representations of the Shapes of Atomic Orbitals
■ What are the shapes of the atomic orbitals? Strictly speaking, an orbital does not have a
definite shape because the wave function extends to infinity. However, while the electron
can be found anywhere, there are regions where the probability of finding it is much higher.
■ Figure (a) shows the electron density distribution of a 1s electron around the nucleus. Note
that it does not have a well-defined boundary; the more dots, the darker the shade, the
higher the probability of finding the electron in that region. Also note that the probability
distribution is spherical. We can draw a boundary surface that will enclose 90% of the total
electron density in the orbital as shown in Figure (c). This will result in a boundary surface
diagram of the 1s orbital as shown in Figure (d).

(c) (d)
Figure (d) shows that all the s orbitals are spherical in shape but differ in size, which
increases as the value of n increases.
The p orbitals starts when n =2 for which ℓ has a value of 1 and mℓ has values -1, 0, +1.
Therefore, there are three 2p orbitals: 2px, 2py, 2pz indicating the axes along which they
are oriented. For the p orbitals, the electron probability density is not spherically symmetric
but has a double teardrop shape, or in some books, a dumbbell shape. The greatest
probability of finding the electron is within the two lobes of the dumbbell region; it has zero
probability along the nodal planes found in the axes. All three 2p orbitals are identical in
shape and energy but differ in orientation as shown in Figure (e). The p orbitals of higher
principal quantum numbers have similar shapes.

(e)
■ Figure (f) shows the d orbitals occur for the first time when n = 3. The
angular function in these cases possesses two angular (or planar) nodes.
Four of the orbitals have the same basic shapes except for the orientation
with respect to the axes. The wave functions exhibit positive and negative
lobes along the axes and shows zero probability of finding the electron at
the origin. The fifth wave function, dx2 , has a similar shape with that of
the p-orbital with a donut-shape region along the x-axis.

(f)
Answers:
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