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The Wave Nature of Light

Light travels through space as a wave - a disturbance that transmits energy through a medium.

Electromagnetic radiation - a form of energy transmission through vacuum or a medium in

which electric and magnetic fields are propagated as a wave. It carries energy through space and
is therefore also known as radiant energy.

Figure 4.2 Characteristics of a wave

Relationship between Wavelength and Frequency

where: c (speed of light) = 3.0 x 108 m/s

When light is passed through a transparent medium such as a prism, the “white” light is refracted
or dispersed into an unbroken or continuous band or spectrum of colors as a rainbow -
ROYGBIV.
Figure 4.1 The electromagnetic spectrum

Classical Descriptions of Matter

Visible region - portion of the electromagnetic spectrum within the wavelength range of 400 -
750 nm that we can perceive as color. John Dalton (1803) - atoms are hard, indivisible particles. Atoms have distinct masses that
distinguish one type of atom from another. All atoms of same element are the same.

Waves have the following characteristics:

J.J. Thomson (1890s) - discovered charge-to-mass ratios of electrons; atoms are divisible
1. Wavelength, λ - distance between two identical points of the wave because the electrons are one part of atom.
2. Frequency, ν - the number of troughs or crest that passes through a given point per unit of
time.
3. Amplitude, A - relates to the intensity of radiation.

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Ernest Rutherford (1910) - shot positive alpha particles at a thin foil of gold from which he Dual nature of matter (Louis de Broglie) - The electron can be imagined as both particle (it
discovered the atomic nucleus. has mass) and a wave (it moves rapidly) and either of these two natures can become
predominant at a given time.

James Maxwell (1873) - visible light consists of electromagnetic waves.

If light can behave like a wave and a particle, matter also (electron) can behave like waves. If
electron behaves like a standing wave, it can only have specific wavelengths and specific
Transition between Classical and Quantum Theory frequencies and thus, energies:

Max Planck (1900) - noted matter did not emit energy in continuous bursts but in whole-number
multiples of certain well-defined quantities.
For wave: For matter:

Quantum theory - Matter absorbs or emits energy in bundles or “quanta.” Radiant

Combining the two equations, we can solve for the wavelength for any matter.
energy is quantized, it is limited to a discrete set of specific values. The smallest amount of
energy that can be emitted or absorbed as electromagnetic radiation is called quantum.

De Broglie relation: where: m = mass in kg

Energy is proportional to the frequency, ν, and wavelength, λ, of radiation, and the
ν = velocity m/s
proportionality constant h which is called Planck's constant.

where: h = 6.63 x 10-34 Js This relation is true for all matter whether microscopic or macroscopic.

Radiant energy may be considered to consist of fluctuating electric and magnetic fields which Illustration:
travel through space in a wavelike motion. It may be described in two ways: 1. A baseball with a mass of 0.143 kg is thrown towards a batter at a velocity of 42.5 m/s.
a. Calculate the wavelength in m associated with the baseball’s motion.
1. Waves of photons - possessing wave-like properties.
2. Stream of photons - possessing particle-like properties.

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b. How does the wavelength compare in size to the baseball (diameter = 0.08 m)? 3. When the atom absorbs energy, an electron can jump from a lower energy level to a higher
The baseball’s wavelength is very much less than its diameter. energy level. The electron is said to be in the excited state when the electron is in a higher
energy orbit (n = 2, 3, 4, etc.).
4. When an electron falls back to the lower level, it emits a definite amount of energy in the
form of a quantum of light.
2. Calculate the wavelength in m associated with an electron traveling at the same velocity. (The
mass of the electron is 9.1095 x 10-31 kg.)
Limitations of the Bohr Model - Quantum Mechanical Model

Unfortunately, the Bohr Model failed for all other elements that had more than one proton and one
electron. (The multiple electron-nuclear attractions, electron-electron repulsions, and nuclear
repulsions make other atoms much more complicated than hydrogen.)
The wavelength of the electron is much larger than its diameter.

In 1920s, a new discipline, quantum mechanics, was developed to describe the motion of
Thus, although all matter can have wave properties, such properties are only submicroscopic particles confined to tiny regions of space. Quantum mechanics makes no attempt
significant for microscopic particles. to specify the position of a small particle at a given instant or how the electron got there. It only
gives the probability of finding small particles - just like taking snapshot of a location and
estimating where greatest number of people is likely to be, it takes a snapshot of the atom at
different times and “see” where the electrons are usually found.

Bohr model of a hydrogen atom (Neils Bohr, 1913) - The electron of the atom can exist only
in certain circular orbits around the nucleus in certain specific radii. Heisenberg’s uncertainty principle - It is impossible to determine accurately both the exact
position and momentum of a particle simultaneously.

“Tennis ball and stairs” analogy for electrons and energy levels, respectively - a ball can bounce up
to or drop from one stair to another but it can never be halfway between two levels. Erwin Schrödinger (1926) - developed a differential equation that allows us to find the
electron's wave function, ψ which ultimately allows us to determine the probability of finding the
electron in a given place.
According to the Bohr’s model:

1. The electron has a definite energy characteristic of the orbit in which it is moving (like the
Probability density for an electron - called the “electron cloud” which dictates the shape of
planetary model of the solar system).
2. When the electron of an atom is as close to the nucleus as possible, it is in a state of lowest the area where the electron resides. Regions where there is a high probability of finding the
possible energy called the ground state. The ground state is the lowest energy state for electron are said to be regions of high electron density.
atom when the electron is in most stable orbit.
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2. Azimuthal quantum number, l - defines the shape of the orbital. It describes the
energy level of the subshells. The number of subshells in a shell is equal to n.
Schrodinger equation - describes an electron in an atom by a mathematical expression called a It has any integral value starting from 0 → (n - 1).
wave function, ψ.

It determines the following:

1. The shape of the orbital the electron occupies

2. The energy of the electron in the orbital
3. The probability of finding the electron in some region

The complete solution to Schroedinger’s equation yields a set of wave functions called orbitals Table 4.1 Azimuthal quantum number values
and their corresponding energies. Each orbital describes a specific distribution of electron density
l values Symbol No. of orbitals Shape
in space.
0 s 1 spherical

1 p 3 dumbbell
Quantum numbers - dimensionless numbers which completely describe the state of an
electron. Four quantum numbers describe distribution and behavior of electrons in atoms. Each 2 d 5 four-lobe
wave function, ψ, corresponds to a set of three quantum numbers and is referred to as an atomic
orbital. 3 f 7 eight-lobe

The four quantum numbers:

1. Principal quantum number, n - describes the distance between the nucleus and the
shell. A shell is the level to which the electrons belong - as n increases, on the average, the
electron is found farther out of the nucleus. It also describes the energy level of the shell - as s orbital
n increases, the energy of the electron increases and is therefore less tightly bound to the
nucleus.
The principal quantum number, n can have integral values 1, 2, 3, etc.

The number of electrons that can be accommodated in a given shell is equal to 2n2.

p orbitals
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Each subshell consists of a set of orbitals. All the orbitals in the same subshell have the same
energy. So within a given shell, the energies of electrons in the orbitals increase in the
following order: ns < np < nd < nf.

c. Magnetic quantum number, ml - determines the spatial orientation of an orbital (the

axes/planes to which the orbital is oriented). It has an integral value of +l, … 0, … ,-l.

d. Spin quantum number, ms - describes the direction of spin of an electron about its own
axis: counterclockwise, ms = -½; and clockwise, ms = +½.
Electrons with the same spin quantum numbers are said to have parallel spins while
those with different ms values are said to have opposite spins.

d orbitals

Table 4.2 Relationship among n, l, ml values through n = 4

l Subshell No. of Total no. of

n value designatio ml values orbitals in orbitals in
s n subshell subshell

1 0 1s 0 1 1
f orbitals
2 0 2s 0 1 4

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1 2p 1, 0, -1 3

3 0 3s 0 1 Electronic Configuration of an Atom

1 3p 1, 0, -1 3 Electronic configuration - the arrangement of electrons in the orbital of an atom.

2 3d 2, 1, 0, -1, -2 5 9 It is described by:

4 0 4s 0 1 a. a number that designates the number of principal shell

b. a letter that designates the subshell (orbital)
1 4p 1, 0, -1 3 c. a superscript that designates the number of electrons in that particular subshell (orbital)
e.g. 2p4 indicates 4 electrons in the p subshell of the 2nd shell
2 4d 2, 1, 0, -1, -2 5
3d8 indicates 8 electrons in the d subshell of the 3rd shell
3 4f 3, 2, 1, 0, -1, -2, -3 7 16

Guidelines:

1. Aufbau (building-up) principle

EXERCISE 4.1 Electrons are distributed in orbitals of increasing energy levels where the lowest energy
orbitals are filled first. Once an orbital has the maximum number of electrons it can hold, it is
1. a. What is the designation for the subshell with n = 5 and l = 1? considered “filled.” Remaining electrons must then be placed into the next highest energy
b. How many orbital are in this subshell? orbital, and so on.
c. Indicate the ml values for each of these orbitals.
2. What is the maximum number of electrons that can occupy the each of the following The orbitals in order of increasing energy:
subshells:
a. 3d c. 2p 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d
b. 4s d. 5f < 7p
3. Give the subshell designation for:
a. n = 3, l = 1 c. n = 2, l = 0
b. n = 6, l = 4 d. n = 4, l = 3
4. Give the complete set of quantum numbers for the following:
a. 2p2 d. 4s1
b. 3d4 e. 5f3
c. 4p 6
f. 5d9

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Figure 4.5 The Aufbau principle To do this, distribute electrons with same spin (up or down) and do not pair electrons until all
subshells have an electron.

For example, the electron configuration of carbon is: 1s2 2s2 2p2.
2. Pauli’s exclusion principle - No two electrons in the same atom can have the same set of
four quantum numbers. That is, the maximum number of electron in an orbital is limited to The orbital diagram can be shown in the following ways:
two and the two electrons in the same orbital must have opposite spins.

For 1s orbital: one electron: n = 1, l = 0, ml = 0, ms = +½

another electron: n = 1, l = 0, ml = 0, ms = -½

For example, with the helium atom, there are three ways to represent two electrons in 1s orbital

(where spin is represented with the electron pointing up or down):

But from Hund's rule, we know (c) would be the most stable.
But the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same
orbital with the same spin.

An orbital can hold a maximum of two electrons: Orbital diagrams of some elements
● An s orbital can hold up to 2 electrons. Total Orbital diagram Valence
● A set of p orbitals can hold up to 6 electrons. Elemen Electronic
electron 3
electron
● A set of d orbitals can hold up to 10 electrons. t 1s 2s 2p configuration
s s s
● A set of f orbitals can hold up to 14 electrons.
3. Hund’s rule - Every orbital in a subshell (degenerate orbitals - same energy) is occupied
H 1 ↑ 1s1 1
with one electron first before any one orbital is doubly-filled and all electrons in
singly-occupied orbitals have the same spin. He 2 ↑↓ 1s2 2
The most stable arrangement of electrons in subshells has the greatest number of
parallel spins. Li 3 ↑↓ ↑ 1s2 2s1 1

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Be 4 ↑↓ ↑↓ 1s2 2s2 2 a. Ca d. Mo
b. Al e. As
B 5 ↑↓ ↑↓ ↑ 1s2 2s2 2p1 3 c. Sr

C 6 ↑↓ ↑↓ ↑ ↑ 1s2 2s2 2p2 4

2. Determine whether the following elements are diamagnetic or paramagnetic by drawing the
N 7 ↑↓ ↑↓ ↑ ↑ ↑ 1s2 2s2 2p3 5 orbital diagram of the valence shell. Determine also the number of valence electrons.
a. O d. Zn
Ne 10 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 1s2 2s2 2p6 8 b. Br e. Mg
c. Ti
Na 11 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ 1s2 2s2 2p6 3s1 1

Valence electrons - outer shell electrons.

Exceptions to the Building-Up Principle

Atoms gain extra stability when their d subshells are half-filled or completely filled.

If we can fill or half-fill a d subshell by promoting an electron from an s orbital to a d orbital, we

Isoelectronic - atoms or ions of different elements that have the same electronic configuration. do so to gain the extra stability.

For example, O2-, F-, Ne, Na+, and Mg2+ have a total number of electrons which is equal to 10. If
this is so, hence, they have the same electronic configuration 1s2 2s2 2p6 and are therefore
For example, chromium has a total number of electrons equal to 24. Its electron configuration is
isoelectronic.
1s2 2s2 2p6 3s2 3p6 4s2 3d4. The orbital diagram of the valence shell is as follows:

Magnetic behavior - the effect of magnetic field on an atom.

1. Diamagnetism - atoms with completely paired electrons which are slightly affected by
magnetic field.
2. Paramagnetism - atoms with unpaired electrons which are greatly affected by magnetic
field.

However, chromium assumes a more stable configuration by promoting one 4s electron to the 3d
subshell to attain half-filled stability. Its actual configuration becomes 1s2 2s2 2p6 3s2 3p6 4s1
3d5 with an orbital diagram of the valence shell as shown.
EXERCISE 4.1

1. Give the electronic configuration of the following elements:

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Similarly, silver assumes a more stable configuration by promoting one 4s electron to the 3d
orbital via completely filled stability. From 1s2 2s2 2p6 3s2 3p6 4s2 3d9, its actual configuration
becomes 1s2 2s2 2p6 3s2 3p6 4s1 3d10.

Writing Electron Configurations Using the Periodic Table

The periodic table's shape actually corresponds to the filling of energy sublevels.

Figure 4.7 The periodic table showing the different sublevels

Abbreviated Electron Configurations

Since noble gases are at the end of each row in the periodic table, all of their electrons are in
filled orbitals. Such electrons are called core electrons since they are more stable (less reactive)
when they belong to completely filled orbitals.

Noble gas core notation - noble gas electron configurations can be used to abbreviate the core
electrons of all elements.

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[He] = 1s2 1. O 4. Fe3+

2. Cd 5. Cu+
[Ne] = 1s2 2s2 2p6 3. Ge2- 6. Sr
[Ar] = 1s2 2s2 2p6 3s2 3p6
7. Give the set of quantum numbers that describe the 4th electron in the 3p subshell.
[Kr] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6

[Xe] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6
8. Give the set of quantum numbers that describe the last electron in the following elements:
a. Mg d. Cu
b. Se e. Br
EXERCISE 4.2 c. Ne f. Al

Give the noble gas core notation of the following elements:

9. How many electrons can be placed in
1. Fe a. shell where n = 3
2. Cd b. shell with n = 4 before the first electron enters the shell with n = 5
3. Ni
4. Au

5. Y

ADDITIONAL EXERCISES

In each of the following,

a. Write the electronic configuration.

b. Write the noble gas core notation.
c. Determine the quantum number describing the last electron.
d. Identify the number of unpaired electrons and indicate whether it is paramagnetic or
diamagnetic.
e. State the number of valence electrons.

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