Atomic Orbitals

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An atomic orbital is a mathematical function that describes the behavior of electrons. Electrons
act as both waves and particles which is known as wave-particle duality. Relating to this,
the Heisenberg uncertainty principle states that there is limited precision when trying to locate an
electron. The atomic orbitals give us the probability of finding an electron at a specific region of
an atom. More specifically, atomic orbitals can describe the quantum states of an electron in the
electron cloud around the atom. The position of an individual electron can be described by the
four quantum numbers: n, l, ml, and ms. The Pauli exclusion principle states that electrons cannot
possess the same set of quantum numbers.

Quantum Numbers
The positions of the electrons in relation to the nucleus are described by quantum numbers. Each
electron has four quantum numbers that apply to its shell, subshell, orbital, and spin.

Principle Quantum Number (nn)

Shells: n = 1, 2, 3...

The first quantum number is the principle quantum number, n. This describes the energy level
and distance from the nucleus of an electron. The greater this number, the further away from the
nucleus the electrons will reside. Electrons in shells with higher values are farther away and will
have higher enery and less stability than electrons in lower energy shells. The smallest principle
quantum number is 1 and increases by integer increments.

Angular Momentum Quantum Number (ll)

Subshells: l = 0, 1, 2 ... (n-1)

The angular momentum quantum number describes the subshell and shape of an orbital. Orbital
names include s, p, d, f, g, h... where 0=s, p=1, etc. The standard periodic table contains
elements with s, p, d, and f orbitals. The values of the angular momentum quantum numbers
range from 0 to n-1. For example, a hydrogen atom's electron in the ground state would have a
n=1 value and therefore must have an l=0 value. This means that the electron is located in the s
subshell within the first orbital. The shape of an s orbital is shown below. The next orbital, n=2,
contains a s (l=0) and a p (l=1) subshell. The shape of a p orbital is shown below, which can be
configured in 3 different orientations in space: along the x, y and z axis. The next orbital, n=3,
contains an s, p, and d (l=2) orbital. The shape of a d orbital is shown below, which has five
different orientations in space. The orientations in space are determined by the next quantum
number.

An s orbital One of the three possible p orbitals One of the five possible d
orbitals

Magnetic Quantum Number (mlml)

ml=...(-l)...-1,0,+1...(+l)

The magenetic quantum number, or orbital, describes the orientation of the orbital in space. That
means it describes whether the part of the electron lies mostly on the x,y, or z axis of the three
dimensional grid. The values of the magnetic quantum number are the negative and positive
values of l. As described above, the s subshell has one orientation, since it is spherical and l=0.
The p subshell has three orientations, represented by ml= -1, 0, 1. The d subshell has five orbitals
represented by ml= -2, -1, 0, 1, 2.

Magnetic Spin Number (msms)

ms= -1/2, +1/2

For every possible n and s value combination, two spins values are possible: a negative spin and
the other electron with a positive spin.

Outside links
 http://en.wikipedia.org/wiki/Atomic_orbitals
 http://www.chemguide.co.uk/atoms/pro.../atomorbs.html
 http://www.youtube.com/watch?v=QREOi94I6Pk
 Orbitals: http://www.youtube.com/watch?v=yBrp8uvNAhI&feature=youtube_gdata

References
1. Timberlake, Karen C. Chemistry : An Introduction to General, Organic, and Biological
Chemistry. 10th ed. Prentice Hall Higher Education, 2008.
2. Petrucci, Ralph H. General Chemistry: Principles and Modern Applications.9th ed. New
Jersey: Pearson Education Inc. 2007.

Problems
1. Write an orbital designation corresponding to the quantum numbers n=3, l=1 and ml=1
2. Write an orbital designation corresponding to the quantum numbers n=4. l=2 and ml=0
3. Can an orbital have the quantum numbers n=2, l=2, and ml=2?
4. For an orbital with n=3 and ml=1, what is (are) the possible value(s) of l?
5. The principal quantum number is the quantum number denoted by n and
which indirectly describes the size of the electron orbital. It is always
assigned an integer value (i.e., n = 1,2,3,...), but its value may never be
0. An orbital for which n = 2 is larger, for example, than an orbital for
which n = 1. Energy must be absorbed in order for an electron to be excited
from an orbital near the nucleus (n = 1) to get to an orbital further from the
nucleus (n = 2).
6. The principal quantum number is cited first in the set of four quantum
numbers associated with an electron. The principal quantum number has
the greatest effect on the energy of the electron. It was first designed to
distinguish between different energy levels in the Bohr model of the
atom but remains applicable to the modern atomic orbital theory.
7. Electrons in an atom occupy regions known as orbitals, and these orbitals have shapes. In
this lesson, we will discuss the secondary quantum number: the angular momentum
quantum number, which determines the shape of an orbital.

8. Angular Momentum Quantum Number

9. There are four quantum numbers that make up the address for an electron. Of the four
quantum numbers, our focus for this lesson is the angular momentum quantum number,
which is also known as the secondary quantum number or azimuthal quantum number.
10. The angular momentum quantum number is a quantum number that describes the 'shape' of
an orbital and tells us which subshells are present in the principal shell. We can think about it
this way: each of our homes has its own architecture. In the subatomic level, the 'home' of
electrons is an orbital, and each orbital has its own shape. The symbol that is used when we
refer to the angular momentum quantum number looks like this:

11. Electrons occupy a region called 'shells' in an atom. The angular momentum quantum
number, l, divides the shells into subshells, which are further divided into orbitals. Each value
of l corresponds to a particular subshell. The lowest possible value for l is 0. This following
table shows which subshells correspond to the angular momentum quantum number:
 12. The angular momentum quantum number can also tell us how many nodes there are in an
orbital. A node is an area in an orbital where there is 0 probability of finding electrons. The
value of l is equal to the number of nodes. For example, for an orbital with an angular
momentum of l = 3, there are 3 nodes.

13. Relationship with Principal Quantum Number

14. It is important to point out that there is a relationship between the principal quantum number
and the angular momentum quantum number. To recap, the principal quantum
number tells us what principal shells the electrons occupy. It determines the energy level
and size of the shell and uses the symbol n and is any positive integer.
15. The angular momentum quantum number values range from 0 to n - 1, and cannot be
greater than n. This table shows the relationship between the two quantum numbers:

Definition: The angular momentum quantum number, ℓ, is the quantum

number associated with the angular momentum of an atomic electron. The
angular momentum quantum number determines the shape of the
electron's orbital.

Also Known As: azimuthal quantum number, second quantum number

Examples: A p orbital is associated with an angular momentum quantum

number equal to 1.
 Spin Quantum Number
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The Spin Quantum Number (msms) describes the angular momentum of an electron. An electron
spins around an axis and has both angular momentum and orbital angular momentum. Because
angular momentum is a vector, the Spin Quantum Number (s) has both a magnitude (1/2) and
direction (+ or -).

Each orbital can only hold two electrons. One electron will have a +1/2 spin and the other will
have a -1/2 spin. Electrons like to fill orbitals before they start to pair up. Therefore the first
electron in an orbital will have a spin of +1/2. After all the orbitals are half filled, the electrons
start to pair up. This second electron in the orbital will have a spin of -1/2. If there are two
electrons in the same orbital, it will spin in opposite directions.

Combinations of Quantum Numbers

 The three quantum numbers (n, l, and m) that describe an orbital are integers: 0, 1, 2, 3.
 The principal quantum number (n) cannot be zero. The allowed values of n are therefore
1, 2, 3, 4...
 The angular quantum number (l) can be any integer between 0 and n - 1.
o If n = 3, l can be either 0, 1, or 2.
 The magnetic quantum number (m) can be any integer between -l and +l.
o If l = 2, m can be -2, -1, 0, +1, or +2.
 Orbitals that have same value of principal quantum number form a Shell(n).
 Orbitals within the shells are divided into subshell (l)
o s:l = 0 p:l = 1 d:l = 2 f:l = 3

Questions
1. What is the spin quantum number for Tungsten (symbol W)?
2. What is the spin quantum number for Gold (symbol Au)?
3. What is the spin quantum number for Sulfur (symbol S)?
 Answers
1. What is the spin quantum number for Tungsten (symbol W)?

Tungsten has 4 electrons in the 5d orbital. Therefore 1 electron will go into each orbital (no
pairing). The 4th electron will have a +1/2 spin.

2. What is the spin quantum number for Gold (symbol Au)?

Gold has 9 electrons in the 5d orbital. Therefore the electrons will start to pair up, which means
the 9th electron will pair up, giving it a -1/2 spin.

3. What is the spin quantum number for Sulfur (symbol S)?

Sulfur has 4 electrons in the 3d orbitals. The 4th electron in this orbital will be the first one to
pair up with another electron, therefore giving it a -1/2 spin.

Pauli Exclusion Principle

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The Pauli Exclusion Principle states that, in an atom or molecule, no two electrons can have
the same four electronic quantum numbers. As an orbital can contain a maximum of only two
electrons, the two electrons must have opposing spins. This means if one is assigned an up-spin (
+1/2), the other must be down-spin (-1/2).

Electrons in the same orbital have the same first three quantum numbers,
e.g., n=1n=1, l=0l=0, ml=0ml=0 for the 1s subshell. Only two electrons can have these
numbers, so that their spin moments must be either ms=−1/2ms=−1/2 or ms=+1/2ms=+1/2. If
the 1s orbital contains only one electron, we have one msms value and the electron configuration
is written as 1s1 (corresponding to hydrogen). If it is fully occupied, we have two msms values,
and the electron configuration is 1s2 (corresponding to helium). Visually these two cases can be
represented as
 As you can see, the 1s subshell can hold only two electrons and when filled the electrons have
opposite spins.

Hund's rule: every orbital in a subshell is singly occupied with one electron before any
one orbital is doubly occupied, and all electrons in singly occupied orbitals have the same
spin.

Hund's Rules
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The Aufbau section discussed how that electrons fill the lowest energy orbitals first, and then
move up to higher energy orbitals only after the lower energy orbitals are full. However, there a
problem with this rule. Certainly, 1s orbitals should be filled before 2s orbitals, because the 1s
orbitals have a lower value of n, and thus a lower energy. What about the three different 2p
orbitals? In what order should they be filled? The answer to this question involves Hund's rule.

Hund's rule states that:

1. Every orbital in a sublevel is singly occupied before any orbital is doubly occupied.
 2. All of the electrons in singly occupied orbitals have the same spin (to maximize total
spin).

When assigning electrons to orbitals, an electron first seeks to fill all the orbitals with similar
energy (also referred to as degenerate orbitals) before pairing with another electron in a half-
filled orbital. Atoms at ground states tend to have as many unpaired electrons as possible. In
visualizing this process, consider how electrons exhibit the same behavior as the same poles on a
magnet would if they came into contact; as the negatively charged electrons fill orbitals, they
first try to get as far as possible from each other before having to pair up.

EXAMPLE 1.11.1: NITROGEN ATOMS

Consider the correct electron configuration of the nitrogen (Z = 7) atom: 1s2 2s2 2p3

The p orbitals are half-filled; there are three electrons and three p orbitals. This is because the
three electrons in the 2p subshell will fill all the empty orbitals first before pairing with electrons
in them.

Keep in mind that elemental nitrogen is found in nature typically as dinitrogen, N2, which
requires molecular orbitals instead of atomic orbitals as demonstrated above.

EXAMPLE 1.21.2: OXYGEN ATOMS

Next, consider oxygen (Z = 8) atom, the element after nitrogen in the same period; its electron
configuration is: 1s2 2s2 2p4
Oxygen has one more electron than nitrogen; as the orbitals are all half-filled, the new electron
must pair up. Keep in mind that elemental oxygen is found in nature typically
as dioxygen, O2O2, which has molecular orbitals instead of atomic orbitals as demonstrated
above.

Hund's Rule Explained

According to the first rule, electrons always enter an empty orbital before they pair up. Electrons
are negatively charged and, as a result, they repel each other. Electrons tend to minimize
repulsion by occupying their own orbitals, rather than sharing an orbital with another electron.
Furthermore, quantum-mechanical calculations have shown that the electrons in singly occupied
orbitals are less effectively screened or shielded from the nucleus. Electron shielding is further
discussed in the next section.

For the second rule, unpaired electrons in singly occupied orbitals have the same spins.
Technically speaking, the first electron in a sublevel could be either "spin-up" or "spin-
down." Once the spin of the first electron in a sublevel is chosen, however, the spins of all of the
other electrons in that sublevel depend on that first spin. To avoid confusion, scientists typically
draw the first electron, and any other unpaired electron, in an orbital as "spin-up."

EXAMPLE 1.31.3: CARBON AND OXYGEN

Consider the electron configuration for carbon atoms: 1s22s22p2: The two 2s electrons will
occupy the same orbital, whereas the two 2p electrons will be in different orbital (and aligned the
same direction) in accordance with Hund's rule.

Consider also the electron configuration of oxygen. Oxygen has 8 electrons. The electron
configuration can be written as 1s22s22p4. To draw the orbital diagram, begin with the following
observations: the first two electrons will pair up in the 1s orbital; the next two electrons will pair
up in the 2s orbital. That leaves 4 electrons, which must be placed in the 2p orbitals. According
to Hund’s rule, all orbitals will be singly occupied before any is doubly occupied. Therefore, two
p orbital get one electron and one will have two electrons. Hund's rule also stipulates that all of
 the unpaired electrons must have the same spin. In keeping with convention, the unpaired
electrons are drawn as "spin-up", which gives (Figure 1).

Purpose of Electron Configurations

When atoms come into contact with one another, it is the outermost electrons of these atoms, or
valence shell, that will interact first. An atom is least stable (and therefore most reactive) when
its valence shell is not full. The valence electrons are largely responsible for an element's
chemical behavior. Elements that have the same number of valence electrons often have similar
chemical properties.

Electron configurations can also predict stability. An atom is most stable (and therefore
unreactive) when all its orbitals are full. The most stable configurations are the ones that have
full energy levels. These configurations occur in the noble gases. The noble gases are very stable
elements that do not react easily with any other elements. Electron configurations can assist in
making predictions about the ways in which certain elements will react, and the chemical
compounds or molecules that different elements will form.

Wave-Particle Duality
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In 1923, Louis de Broglie, a French physicist, proposed a hypothesis to explain the theory of the
atomic structure.By using a series of substitution de Broglie hypothesizes particles to hold
properties of waves. Within a few years, de Broglie's hypothesis was tested by scientists shooting
electrons and rays of lights through slits. What scientists discovered was the electron stream
acted the same was as light proving de Broglie correct.

Definition of Wave-Particle Duality

The behaviors of the electron does not allow for it to be observable as a particle and as a wave.
The two sided nature of the electron is known as the Wave-Particle Duality: The property of
particles behaving as waves and the property of waves behaving as particles as well as waves.
Although the duality is not very effective in large matter. The wave characteristic of the electron
implicates many of the electron's particle behaviors.

Planck's Hypothesis of the Quantum Theory states that energy is emitted in quanta, little packets
of energy, instead of a continuous emission. He stated that energy emitted is related to the
frequency of the light emitted. Planck's hypothesis states that a quantum of energy was related to
the frequency by his equation E=hνE=hν.

Waves & Particles Behaviors of Light

An easy way to prove the duality between a particle and a wave is to observe light. At the time,
many scientists believed that light is a wave. Since light is like waves, it has the ability to
diffract, reflect, refract, and interfere etc . . . Yet, light behaved strangely at certain times, and
scientists were befuddled until . . .

Diffraction Interference

Albert Einstein's theory of photoelectric effect contributed greatly to De Broglie's Theory and
was a proof that waves and particles could overlap. Light can also be observed as a particle
known as photon. When light is shown on certain objects, the electrons will be released. Certain
amounts of energy is needed to remove an electron from the surface of a substance. So, if a
photon of greater energy than that of an electron hits a solid that electron will be emitted.
 The following picture also describes threshold Vo, where one photon did not have enough
intensity to throw off an electron.

When the electrons are release, they also release kinetic energy. Classical wave theory states the
greater the intensity the greater the energy. Since energy of a wave is directly proportional to its
amplitude, it was puzzling for scientists to find brighter lights(higher intensity) did not affect its
overall kinetic energy.

However, scientists did discover that frequency of light effectively changed the amount of
kinetic energy. Since certain objects do not emit electrons under certain frequencies, a threshold,
V0, is used. This threshold was used to describe the amount of kinetic energy needed for a photon
to throw off an electron. They arrived at a linear relation for frequency and kinetic energy given
by the rough sketch of
The slope of this line was confirm to be Planck's Constant, h = 6.63 x 10-34

Using the graph, we are given the same equation as before: Ek = hv. Since the energy of waves
and energy of light do not coincide, we can rule that light is a particle that contains the property
of waves.

De Broglie Wavelength
De Broglie derived his equation using well established theories through the following series of
substitutions:

1. De Broglie first used Einstein's famous equation relating matter and energy:

E=mc2E=mc2

E= energy, m = mass, c = speed of light

2. Using Planck's theory which states every quantum of a wave has a discrete amount of
energy given by Planck's equation:

E=hνE=hν

E = energy, h = Plank's constant(6.62607 x 10-34 J s), υ = frequency

3. Since de Broglie believes particles and wave have the same traits, the two energies
would be the same:
 mc2=hνmc2=hν

4. Because real particles do not travel at the speed of light, De Broglie subsituted v,
velocity, for c, the speed of light.

mv2=hνmv2=hν

5. Through the equation λλ, de Broglie substituted v/λv/λ for νν and arrived at the final
expression that relates wavelength and particle with speed.

mv2=hvλmv2=hvλ

Hence:

λ=hvmv2=hmvλ=hvmv2=hmv

Although De Broglie was credited for his hypothesis, he had no actual experimental evidence for
his conjecture. In 1927, Clinton J. Davisson and Lester H. Germer shot electron particles onto
onto a nickel crystal. What they see is the diffraction of the electron similar to waves diffractions
against crystals(x-rays). In the same year, an English physicist, George P. Thomson fired
electrons towards thin metal foil providing him with the same results as Davisson and Germer.

Quantum Theory Made Easy Video: Dr.

Quantum
 De Broglie's Theory can be seen in Young's Double Slit Experiment explained by the
following:

Problems
1. The de Broglie wavelength of an electron is 2.0 x 10-16, find its velocity.

2. A particle with the speed of 2.1 x 107, its de Broglie wavelength is 6.5x10-14. What is the mass
of the particle?

3. Find the energy of a particle that weighs .000300 g and has a de Broglie wavelength of 1.9 x
10-36 m.

4. Determine all of the following frequency, wavelengths, and energy if one is given:

a. frequency = 105 MHz

 b. wavelength = 527 nm

c. energy = 3.20 x 10-17 J

d. frequency = 34.2 x 10 15 Hz

Answers:

1. 3.6 x 10-12

2. 4.9 x 10-28 kg

3. 4.1 x 105 J

4.

a. wavelength: 2.86m, energy: 6.96 x 10 -19 J

b. frequency: 5.69 x 10 14 Hz, energy: 3.77 x 10 -19 J

c. frequency: 4.74 x 10 16 Hz, wavelength: 6.33nm

d. wavelength: 8.77 nm, energy: 2.27 x 10-17 J