Chapter 7- Quantum Chemistry Chang 10th Ed.

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Quantum Theory and the Electronic Structure of Atoms

7.1 From Classical Physics to Quantum Theory

In the late 1800s it was viewed that our knowledge of the physical world was nearly complete
and perfect. We could predict the outcomes of various things in the world using equations from
Newtonian Physics. In short there was nothing else left to know that could be of interest.

Much of this discussion will be based on the observation of energy and matter as waves since the
Newtonian view of the world does not explain what happens to atoms and electrons very well
and the only description which makes any sense is the mathematical representation of these
things as both waves and particles. Also much of this chapter relates to the properties of light
and matter. The reason we will spend so much time on this is that the interaction of light and
matter is one of the ways we gain information about electrons and how they behave around
nuclei in materials. Since we will talk about waves and light we need to have a better
understanding of the terminology for both waves and light in order to understand the relationship
between light and matter.

Waves - Waves are a rhythmic (time dependent and reproducible) oscillation which can transmit
energy. A wave is said to have an amplitude (how high it is), a wavelength (the distance
between repeating points in a cycle), and a frequency (how often the repeating points occur).
Waves also travel with a specified speed (velocity) which is the product of the wavelength and
the frequency. Our discussion of waves will be restricted to light and all light travels at the same
speed of 3.00E08 m/s in a vacuum.

Light is a form of electromagnetic radiation that has certain values of frequency and wavelength
such that the product is the speed of light. Visible light ranges from 400 to 700 nm in
wavelength which corresponds to frequencies of 10E14 per second (Hz).

[Figure 7.4]

c = λν

As the frequency increases l decreases (more blue, higher E). Conversely as frequency decreases
l increases (more red, lower E). There is electromagnetic radiation beyond what we see. The
immediate boundaries are infrared and microwave (heat energy) and UV and X-rays at higher
energy.
Now that we know a little about waves, light and electromagnetic radiation -- Let’s see how 19th
century physics fell apart and what needed to be done to correct it.
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Max Planck (1858-1947) one of the most influential minds of the 20th century - started what
would become the concept of quantum physics.
There were at least three things that we at odds with the equations used to describe things in the
late 1800s.
1) When you heat a solid to various temperatures, it gives off heat (of course) but also light
and the color of light (wavelength) depends on the temperature. If something is just hot
enough to glow it is red-orange but at 1400 degrees C it is “white hot”. This could not be
explained by “modern physics” in 1890.
2) Photoelectric effect described later there is a wavelength dependence on the transfer of
electrons in a certain apparatus
3) When you look at these glowing solids there is broad band radiation but when you look
carefully at the sun or burn metal salts in a flame there are lines of energy at specific
wavelengths not a continuum.

Planck presented the view that energy when absorbed or emitted by atoms was quantized
which means it comes not in a continuous series of values but in discrete “packets” with certain
values related to integer numbers (later called quantum numbers). Thus E=hν or nhν where n is
an integer, h is a constant (Planck’s constant) and ν is the frequency. In other words the energy
emitted (or absorbed) by an atom is only at certain values of frequency (and therefore
wavelength) like the difference between an old radio dial and a digital tuner.

7.2 The Photoelectric Effect

When light is shining on the metal electrons can be ejected from the metal but only at a certain
wavelength of light or shorter (threshold). Light at longer wavelengths could not give this result
even if allowed to shine of the metal for an extended period of time.

[Figure 7.5]
Einstein used Planck’s theory of quanta and added the concept that light must be considered like
a particle of a given energy (called a photon).
Thus light behaves like a wave and also as a particle -- this is called the wave particle duality of
matter. That sometimes we need to describe these as particles and sometimes as waves but they
are both at the same time and neither one exclusively although we may need to take one extreme
to explain a given phenomenon.

7.3 Bohr’s Theory of the Hydrogen Atom

Hydrogen atom: 1 proton and 1 electron - the simplest atom.

When observed using a discharge tube

[Figure 7.6]

you observe 4 lines (Red Green Blue Violet) which must be related to these simple quantum
numbers. JJ Balmer determined that the relationship between wavelength and n was 1/λ = K
(1/22 - 1/n2) which gives n=3 656nm, n=4 486 nm, n=5 434 nm, n=6 410 nm) or again the energy
is quantized and not continuous.
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Bohr’s Postulates

1) Energy Level Postulate: Electrons exist at specific energy levels related to whole numbers
called the principle quantum number
2) Energy changes (light absorption or emission) occur when electrons move from one energy
level (one set of quantum numbers) to another

In a formula: ΔE = hν = RH (1/nf2 - 1/ni2) or 1/λ = RH/hc (1/nf2 - 1/ni2)

Where RH is a constant for hydrogen and n is the quantum number

Why would this be for n=2 and not n=1? Wouldn’t this be higher in energy than we would
expect? Yes,

[Figure 7.11] shows that the n=2 transitions are only the ones we can see. There are higher
energy n=1 and lower energy n=3, 4 which are in the UV and IR respecively. [Table 7.1]

These calculations are much more difficult for any non H system (more than one electron).
What is also true is that other elements exhibit line emission spectra which also shows that the
energies are defined by simple integers (quantum numbers). [Figure 7.8]

7.4 The Dual Nature of the Electron

If light can behave like a particle can electrons behave like a wave? This general solution was
found by Louis De Broglie who showed that all particles can behave as waves where the
wavelength is related to the particle’s momentum. λ = h/mu. This is a general relationship for
all matter.

7.5 Quantum Mechanics

There is a limit to our ability to measure the position and speed of a small particle. This limit is
called the Heisenburg Uncertainty Principle which states that you cannot simultaneously know
both the position and the momentum of a particle. In other words, if you know exactly where it
is you cannot know how fast it is traveling; if you know its velocity, you cannot accurately
determine where it is.

Quantum mechanics mathematically describes electrons as waves (called the wave function ψ)
but spatially can only describe electrons as a function of statistical probability. The equation for
the energy of an electron is the wave function; the probability is the square of this function.
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Conclusions about quantum chemistry

1) Electrons are particles but can behave like waves just as light consists of waves but can
behave like particles. This is always true for small particles at high velocities and the
particles have both particle and wave properties.
2) Your cannot know the position and momentum of an electron precisely at any given point
in time.
3) Electrons in an atom exist in quantized energy states which are defined mathematically as
wave functions. The probability of finding an electron within a certain volume around
the nucleus is the wave function squared also called an atomic orbital.

Because we cannot know the position of an electron directly we have to resort to talking about
the electron as a probability function. We can also call this electron density - the probability of
finding an electron in a given region of space relative to the nucleus. This electron density for an
atom which relates to the quantized energy of the electron (as we know it must) is called an
atomic orbital (not orbit).

Atomic orbital: The 3-D space defined by a set of quantum numbers which specify its energy
where an electron has a high probability of being when the electron is part of an atom. An
atomic orbital has a defined 3-D volume and a quantized energy (energy defined by some simple
integers).

[Figure 7.18]

The mathematics of these types of probability functions cannot be solved if there are interacting
electrons -- in other words we can perform the math only for a hydrogen atom (not even a
hydrogen molecule!) It turns out that we can adjust the energies for hydrogen atomic orbitals
(note that as the Balmer series shows one atom can have an electron in different energy levels)
and use them for more complicated electronic systems.

7.6 Quantum Numbers

When we talk about atomic orbitals we said that they define a given volume (relative to the
nucleus) and correspond to a certain energy level which is quantized. We will use quantum
numbers to define both of these properties for each electron in an atom.

Every electron in a atom will be defined by four quantum numbers

n - the principle quantum number or main quantum number
l - angular momentum quantum number
ml - the magnetic quantum number
ms - the spin quantum number

We will look at what each of these quantum numbers tells us about the probability of finding an
electron in a given region of space and what it tells us about the energy. The more stable an
orbital, the lower in energy it is; the less stable the higher in energy it is.
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n - Principle quantum number or main quantum number

Defines the (gross) energy level and defines how close an atom is to the nucleus. The
possible values of n are 1 to n (simple whole integers greater than zero). If the n value is
large the electron is in a high energy orbital far away from the nuclues; if n is small the
electron is in a low energy orbital close to the nucleus.

l - angular momentum quantum number

Defines the shape (in 3-D space relative to nucleus) of an orbital. Possible values of l are
0 to n-1. The l values also give a fine tuning of energy for multi-electron systems (not
hydrogen atoms). It turns out that the lower the value of l the lower in energy the orbital
is even if they have the same value for n. Note also the the possible values of l increase
as n increases - in other words the probability functions become more complex as the
distance from the nucleus increases.

ml - magnetic quantum number

Defines the orientation in space (x,y,z axis orientation - or polar coordinate orientation)
which does not effect the energy of the orbitals if they have the same n and l values. The
possible values are -l to +l. Again the possible values for l increase and the distance from
the nucleus increases (these probability functions become more complex)

ms - spin quantum number

Defines the spin direction of an electron. Electrons have a property which is analogous to
a charged particle spinning in a given direction. This is shown in the interaction of bound
electrons with magnetic fields
[Figure 7.17]
The ms value can be 1/2 or -1/2 only relating to clockwise and couterclockwise spinning.
This value has a small but measurable impact on the energy level.

The relative energies of some bound electrons can be determined by placing a sample in a
magnetic field in ESR experiments.
Of greater importance is the fact that nuclei also show this interaction of spin and magnetic fields
and organic chemistry uses this greatly in what is called NMR experiments.
Applications to biological systems where the spin of hydrogen nuclei in water in biological
samples (cells, rats, humans) is called MRI.

There is a shorthand way of defining the l quantum number (which relates to shape and energy)
and will be more common for us in the rest of the course. An orbital with l = 0 is called an s
orbital (if n=3 and l=0 then it is a 3s orbital); l =1 is a p orbital, l=2 is a d orbital; l = 3 is an f
orbital; l = 4 is a g orbital. Thus we will refer to n and l often in this shorthand notation.

[Table 7.2]

Each electron in an atom will be defined by these four values. Let’s see what kind of values can
be found and what they mean. Remember that as n increases there are more possible values for
the others.
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n=0, l = 1, ml = 0 ms = 1/2 not possible because n must be greater than 0

n=2, l = 1 , ml = 0, ms = 1/2 these are possible n<0, l = n-1; 2p orbital
n= 4, l =3, ml = -3, ms = -1/2 possible n<0, l = n-1, ml = -l; 4f orbital
note that if n = 4 then l = 0, 1, 2, 3 or 4s, 4p, 4d, 4f; ml is orientation only

Could you have a 2d orbital? n=2 l=2 NO l can only equal n-1
that means the possiblitiy of s, p, d, f that the latter can only occur for higher values of n

Let’s look at the shapes of these orbitals as defined by l -- or what are the shapes of s, p, d, f, and
g orbtials?

7.7 Atomic Orbitals

[Figures of s, p, d, f orbitals, Chang 7.19-7.21]

s orbitals are the simplest orbitals with l = 0. The shapes of these orbitals are the simples
geometry with a spherical probability function. We can say that the s orbital is spherical and for
all s orbitals the ml = 0 (there is no ‘orientation’ since it is an evenly distributed sphere. As n
increases, the radius of the sphere increases and a 4s orbital is bigger than a 2s orbital.

p orbitals are ‘dumb-bell’ shaped and have l = 1 (n must be 2 or greater) with possible ml values
of -1, 0 +1 (3 orbitals) which means there are three ways to orient the three p orbitals. The p
orbitals are directional along an axis. As for the s orbitals as n increases the p orbitals become
larger and further removed from the nucleus.

d orbitals are mostly clover shaped; l = 2 (n=3 or greater) and there are 5 values for ml: -2, -1, 0,
+1, +2 or five d orbitals. The geometery is more complicated here.

f orbitals are even more complicated with l = 3 (n= 4 or greater) and 7 values of ml: -3, -2, -1, 0,
1, 2, 3 or seven d orbitals.

7.8 Electronic Configuration

The electronic configuration is a description of what orbitals are populated with electrons (and
how many of them). This will define n and l for electrons and we will use the shorthand of s, p,
d, f etc. Thus if you have one electron in a 1s orbital we would write the electronic configuration
as 1s1. If you had 3 electrons in 4 f orbitals we would write 4f3.

When we talk about muti-electron systems (who’s interested in only hydrogen atoms) we want to
under stand the rules that electrons obey in filling orbitals. In general what occurs is what you
would expect - Electrons will populate lower energy orbitals (which are closer to the nucleus)
before they populate higher energy orbitals. There are three other considerations before we
develop rules for how these electrons are ‘stacked’ into an atom.
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Pauli Exclusion Principle states that each electron in an atom must have a unique set of four
quantum numbers. This means that if two electrons are present in an orbital that they must have
at least different ms values. Another way of saying this is that no two electrons can be in the
same place at the same time. It also means that each atomic orbital can contain a maximum of
two electrons always.

For hydrogen (1s1) we find that the energies are ranked by n only (l has no effect) but only in this
1 electron system.
[Figure 7.22]
In all other atoms, the l value (s, p, d, f) affects not only the shape but also a “fine tuning” of the
energy. The smaller the value of l the lower in energy the orbital [Figure 7.23] or the 3d is
higher in energy than 3p than 3s. This means that the n values which define energy also can
overlap depending upon the value of l. Thus orbitals which have different values of l are not
equal in energy but the lower the value of l the lower the energy.

We can talk about the population of electrons using an orbital configuration as follows: H atom
1s1, He atom 1s2, Li atom 1s2, 2s1 etc.
Assuming that electrons will add to the lowest energy first followed by the next lowest, etc and
that two electrons can fill each orbital. We can also write this as an orbital diagram. Chang does
not indicate energy when he writes these but I will to show that the energies of the s and p (or 1s
and 2s) are not equal. Put boxes for dashes in Figure 7.23 and you have an orbital diagram for
48 electrons.

Hund’s rule states that if you have more than one electron in orbitals of equal energy (same n and
l) then populate separate orbitals first all with the same spin before pairing up and filling orbitals.
It certainly makes sense that orbitals will fill up separately before two electrons go in because
they would be in separate regions in space. It is more subtle but true that the lower energy state
is when electrons spin are in the same direction. Show orbital diagram of C, N, O, F, Ne as well
as electron config.

De-emphasize para and dimagnetic - paramagnetic means it has unpaired electrons and
diamagnetic has paired electrons. Paramagnetic materials such as LOX are attracted to a magnet.

General Rules for Assigning Electrons to Atomic Orbitals (Chang pg. 305)

1. Each shell or n value has n subshells.

2. Each subshell of l value has 2l+1 orbitals.
3. Only two electrons can be placed in any orbital.
4. The maximum number of electrons in a given n level (not atom!) is 2n2

Let’s talk about how these configurations can be determined relative to the periodic table. First
is that each orbital can have only two electrons (3 above, PEP). Second is that the number of
orbitals in a subshell is 2l+1.
What does that mean?
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l value possible ml total orbitals total electrons

s orbitals 0 0 1 2
p orbitals 1 -1, 0 +1 3 6
d orbitals 2 -2, -1, 0, 1, 2 5 10
f orbitals 3 -3, -2, -1, 0, 1, 2, 3 7 14

Can we find any correlation between the shape of the table and the values above? s-Block (Main
Block), p-Block (Main Block), d-Block (Transition Metals), f-Block (Actinides and Lanthanides)

[Figure 2.10]

The electrons in these regions are the electrons being filled from left to right. [Figure 7.23,
7.27]

7.9 The Aufbau (Building-up) Principle

We said that the s, p, d, f orbitals with the same n have different energies and that the s, p, d, f
energy distribution could expand past the n energy levels. [Figure 7.23; 7.24] We also said
that the electrons will add to the lower energy atomic orbitals first. Thus without knowing these
two facts one might expect that the filling order is 1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, etc. but according
to figure 7.23 that is not true, the electrons fill as in Figure 7.24. Also note that figure 7.24 does
not have to be memorized because we can get the same information directly from the
periodic table.

[Figure 7.28, Table 7.3]

Table 7.3 gives the electronic configurations for all of the elements where there is a shorthand
method using the noble gas core rather than writing out all of the electrons. This is used because
filling a noble gas configuration results in a high stability state called a closed subshell and the
electrons which under reactions are almost always those which have been added after the noble
gas core electrons (valence electrons- the outmost or most reactive electrons). The book talks
about the several exceptions to the relationship bewteen electronic configuration as determined
from the table and the true configuration. For this course if you can correctly identify the
configuration using the periodic table I will mark it as correct even though there are some
exceptions. Thus the true correct answer or the one predicted from the PT will both be correct.
You should be aware that again, this is in order for you to appreciate the usefulness of the table
and in “the real world” there may be exceptions to these rules. Overall the success rate will be
very high if you learn to identify electronic configurations from the table directly. Note also that
the d subshell is one row lower and f is two rows lower than the period. For s and p n is equal to
the period.