Chemistry

Lecture 2-3
The Quantum Mechanical Model of the Atom

Our last experiment demonstrated that the Rutherford-Bohr model of the atom correctly
described the various electronic energy levels within a hydrogen atom. When Bohr
attempted to use his equation to predict the spectral lines of other elements with more
than one electron, the equation failed miserably. Furthermore, closer inspection of the
spectrum of hydrogen under a magnetic field indicated that the spectral lines were not
single lines but a large group of lines finely spaced. It became evident that predicting the
energies of electrons inside of atoms was more difficult than expected.

A physicist by the name of Heisenburg discovered a very important principle with

implications about defining the momentum, p (combination of mass and speed, p=mv),
and the location of a moving object. In effect the Heisenburg Uncertainty Principle states
that it is impossible to know both the exact location and momentum of a moving object at
the same time. The uncertainty in the position (∆x) times the uncertainty in the
momentum (∆p) cannot be zero, specifically the product is greater than or equal to
Planck’s constant divided by 4π.

/ 4π

This uncertainty is very small for large objects moving at small speeds. However the
uncertainty in the location of small objects like electrons moving at large speeds is large;
so large that we have no way of describing precisely the motion of an electron around the
nucleus.

Another physicist by the name of DeBroglie had an interesting idea that helps solve the
dilemma of trying to locate the electron inside of the atom. He noted that the quantum
theory of light implicated that light has particle characteristics (photons) and wave
characteristics (frequency and wavelength). Could this wave-particle duality also include
electrons? He calculated that the wavelength of a particle should be inversely related to
its momentum. In other words, large particles will have wavelengths that are too short to
be measured but small particles, like electrons, should have measurable wavelengths. A
beam of electrons was shown to be diffracted (spread out after passing through an
opening) just like sound waves are diffracted as they pass through a door way allowing
you to hear around the corner. The equation for the wavelength of a particle is given
below.

This equation predicts a wavelength for electrons that matches that measured in the
diffraction experiments. The fact that electrons have a measurable wavelength is used in
the construction of an electron microscope!
Another physicist (gosh these guys must be smart!) by the name of Schrodinger wrote
equations combining both the particle (mass and charge) characteristics of the electron
with its wave characteristics (frequency and wavelength). The solutions to these complex
equations (Schrodinger wave equation) yield the amplitudes (Ψ) that correctly indicate
the possible energy values of electrons in all atoms! Remember that the amplitude of a
wave is its “height”.

While the wave equations correctly predict the energies of electrons inside of atoms, we
still do not have a model of what an atom looks like. It turns out the amplitude values
obtained from the wave equations, when squared, (Ψ2), give the probability of locating
the electron at all positions around the nucleus! We can picture a cloud around the
nucleus of a given radius which describes the positions of maximum probability of
locating the electron. The quantum mechanical model of the atom is also sometimes
called the electron cloud model for this reason. These regions of space around the
nucleus with a high probability of finding the electron are called orbitals.

How are the various energies of electrons described??

The Bohr model introduced a single quantum number, n, to describe an orbit. The
quantum mechanical model uses 3 quantum numbers n, l, and m to describe a particular
orbital.

The principal quantum number, n, can have integral values of 1, 2, 3 and so forth. As n
increases the orbital becomes larger, and the electron spends more time farther from the
nucleus. An increase in n also means that the electron has a higher energy and is
therefore less tightly bound to the nucleus.

The second quantum number, l, can have integral values from 0 to n-1 for each value of
n. This quantum number describes the shape of the orbital or electron cloud. We will
study these shapes later on. Sometimes, instead of numbers the various orbitals are
described by letter s, p, d, and f corresponding to l values of 0, 1, 2, and 3.

Value 0 1 2 3
of l
Letter s p d f
used

The third quantum number, m, can have integral values between l and -1, including zero.
This quantum number describes the orientation of the orbital in space. We will study
these directions later. Think of the third quantum number as an address for a particular
orbital.

All orbitals with the same value of n are called an electron shell. Each set of orbitals that
have the same n and l values are called a subshell or sublevel. The table below
summarizes the relationships between the values of n, l, and m for values of n from 1 to
4.
n Possible Subshell Possible values of m Number Total number of
values of l designation of orbitals in shell
orbitals
in
subshell
1 0 1s 0 1 1=n2
2 0 2s 0 1
1 2p -1,0,+1 3 1+3=4=n2
3 0 3s 0 1
1 3p -1,0,+1 3
2 3d -2,-1,0,+1,+2 5 1+3+5=9=n2
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 1+3+5+7=16=n2

Analysis of this table illustrates several very important conclusions:

1. The number of subshells (sublevels) is equal to the value of n.
2. The number of orbitals in a subshell will always be constant: 1 for s, 3 for p, 5 for
d, and 7 for f.
3. The total number of orbitals in any shell is n2.
4. The maximum electron population in any shell is 2n2.

Orbitals in the same subshell have the same energy (the fancy term is degenerate). For a
given value of n, the energy of the different subshells always follows the order

s<p<d<f
However, the order that the electrons are placed into the atom can be puzzling. The first
energy level (n=1) is filled before electrons go into the second energy level (n=2). The
second energy level is filled before electrons are added to the third energy level (n=3).
However, the third energy level is NOT filled before some electrons are added to the
fourth energy level (n=4). This is because the differences in energy between the energy
levels gets smaller as n increases. The energy levels begin to overlap so that the lower
portion of the fourth energy level has less energy than the upper portion of the third
energy level. You do not have to remember the overlaps. Once we study the periodic
table, you will easily remember where the overlaps occur.

How many electrons can fit into an orbital? It turns out that the maximum capacity of an
type orbital (s, p, d, or f) is two electrons. It can also be shown experimentally that the
two electrons that share a common orbital must bear an important relationship to each
other. Electrons have a property called spin. Each electron can be thought of as a tiny
top that either spins clockwise or counterclockwise. A fourth quantum number, s, the
spin quantum number, can have two values, +1/2 and -1/2, corresponding to these two
directions of spin. Electrons that are in the same orbital must have opposite spins! This
is because each electron is like a tiny magnet with a N and S pole. Opposite spins will
allow the N pole of one electron to be attracted to the S pole of the other electron.
Electrons with opposite spins attract each other.

Any orbital can be described with 3 quantum numbers (n, l, and m). The two electrons in
the same filled orbital share the same value for these three quantum numbers. The fourth
quantum number must be different since the two electrons must have opposite spins to be
in the same orbital. This is summarized by the Pauli Exclusion Principle: No two
electrons in the same atom can have the same set of four quantum numbers. If only one
electron is in an orbital we will assume it has a +1/2 value for the spin quantum number.

Before we start describing the energies of electrons in atoms another important principle
must be studied. Electrons are all negative and therefore they repel each other. Thus, if
electrons have a choice of pairing up or going into an empty orbital of the same energy,
the electron will go into the empty orbital first. Hund’s Rule states that for degenerate
orbitals (orbitals of the same energy), the lowest energy is attained when the number of
electrons with the same spin is maximized.

In our next lab we will learn four different ways of describing the electrons in an atom:
quantum numbers, orbital filling diagrams, electron configurations, and electron dot
diagrams.
Chemistry Name_____________________________
HW 2.3 Period _____ Date______________________
Quantum Mechanical Model

1. What is Hund’s Rule?

2. What is the Pauli Exclusion Principle?

3. What is an orbital?

4. How many electrons can fit in an orbital?

5. What letters are used to represent the various subshells (sublevels) in an atom?

6. Complete the following table:

sublevel number of orbitals

s
p
d
f

7. How are orbitals represented in orbital filling diagrams?

8. How are electrons represented in orbital filling diagrams?

9. What electrons are shown in an electron dot diagram?

10. How many quantum numbers are needed to describe a particular orbital in an
atom?