QUANTUM THEORY &

ATOMIC STRUCTURE
GENERAL CHEMISTRY
by Dr. Istadi

THE NATURE OF LIGHT

Visible light is one type of
electromagnetic radiation
(electromagnetic radiation)
The electromagnetic radiation has the
wave properties:
Frequency (): the number of cycles
the wave undergoes per second ==>
1/second Hz
Wavelength (): the distance
between any point on a wave and the
corresponding point on the next crest
of the wave (the distance the wave
travels during one cycle) ==> m, nm,
(10-10 m)
2

 Speed of light (c): 3 x 108 m/s ==> c = v x

where c is constant
That's mean, radiation with a high frequency has a short
wavelength, and vice versa
Another characteristic of a wave is: AMPLITUDE
Amplitude: the height of the crest of each wave or intensity of the
wave/radiation
The two waves shown have the same wavelength (color) but
different amplitudes, and therefore different brightnesses
(intensities)
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The Electromagnetic Spectrum

Visible light represents a small portion of the continuum of radiant

energy, known as electromagnetic spectrum
All the waves in the spectrum travel at the same speed through a
vacuum but differ in frequency and therefore wavelength
Wavelength of visible light as different colors: from red (=750 nm) to
violet (=400 nm)
Light of single wavelength is called MONOCHROMATIC
Light of many wavelength is called POLYCHROMATIC

Distinction Between Energy and

Matter

In contrast, a particle does not

undergo refraction when passing a
boundary

when light wave passes from air to

water, the speed of the wave changes
==> refraction
After strikes the boundary, the light
continues at a different angle,
therefore change in speed and
direction
The new angle depends on the
materials on either side of the
boundary and the wavelength of the
light
White light is dispersed into its
component colorsm when pass
through a prism, because each
incoming wavelength is refracted at a 5
slightly different angle.

 If waves of light pass through two adjacent slits, the emerging circular
waves interact with each other through the process of interference.
If the crests of the waves coincide (in phase), they interfere
constructively and the amplitudes add together.
If the crests coincide with throughs (out of phase), they interfere
destructively and the amplitudes cancel.
the result is a diffraction pattern of brighter and darker regions
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The Particle Nature of Light

1.Blackbody Radiation
2.The Photoelectric effect
3.Atomic Spectra

Blackbody Radiation
When a coal is heated to 1000 K ==> emit visible light (red glow)
At 1500 K, the light is brighter and more orange, like that from an
electric heating coil (elemen pemanas listrik)
These changes in intensity and wavelength of emitted light as an
object is heated are characteristic of blackbody radiation.
In 1900, Max Planck ==> hot or glowing object could emit or
absorb only certain quantities of energy:
E = nhv
E: energy of radiation (J); v : frequency (s-1); n : positive integer of a
quantum number; h : proportionality constant (Planck's constant in
J.s)
h = 6.62606876 x 10-34 J.s = 6.626 x 10-34 J.s
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Quantum Energy

If an atom itself can emit only certain quantities of energy ==> the
atom itself can have only certain quantities of energy
Thus, the energy of an atom is quantized
Each change in the atom's energy results from the gain or loss of one
or more packet (amount) of energy.
Each energy packet is called a quantum (= hv)
An atom changes its energy state by emiting (or absorbing) one or
more quanta, and the energy of the emitted (or absorbed) radiation is
equal to the difference in the atom's energy states:
Eatom = Eemitted (or absorbed) radiation = nhv
The atom can change its energy only by integer multiples of hv ==>
the smallest changes occurs when an atom in a given energy state
changes to an adjacent states when n=1

E = hv
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Photoelectric Effect and Photon

Theory of Light
When monochromatical light of high
enough frequency strikes the metal plate,
electrons are freed from the plate and
travel to the positive electrode, creating a
current
Plank's idea of quantized energy ==>
Einstein: light itself is particulate, that is
quantized into small bundles of
electromagnetic energy ==> PHOTONS
Planck ==> each atom changes its energyu
whenever it absorbs or emits one photon,
one particle of light, whose energy is fixed
by its frequency:
Ephoton = hv = Eatom

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How Einstein's Photon Theory

Explains the Photoelectric Effect?
According to the photon theory, a beam of light consists of an enormous
number of photons.
Light intensity is related to the number of photons striking the surface per
unit time, but not to their energy.
Therefore, a photon of a certain minimum energy must be absorbed for
an electron to be freed.
Since energy depends on frequency (hv), the theory predicts a threshold
frequency.
An electron can not save up energy from several photons below the
minimum energy until it has enough to break free.
Rather, one electron breaks free the moment it absorbs one photon of
enough energy.
The current is weaker in dim light than in bright light because fewer
photons of enough energy are present, so fewer electrons break free per
unit time.
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But some current flows the moment photons reach the metal plate

Examples of Energy Radiation

A cook uses a microwave oven to heat a metal. The wavelength
of the radiation is 1.20 cm. What is energy of one photon of this
microwave radiation?
Solution:
E = hv = hc/

(6.626x10-34 J.s)(3.00x108 m/s)

= -------------------------------------------
(1.20 cm)(10-2 m/cm)

= 1.66x10-23 J

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ATOMIC SPECTRA
What happen when an element is vaporized and then
electrically excited?
Light from excited Hydrogen atoms pases through a
narrow slit and is then refracted by a prism.
This light does not create a continuous spectrum, or
rainbow, as sunlight does
Instead, it creates a line spectrum, a series of fine lines of
individual colors separated by colorless spaces (black)
The wavelength of these spectral lines are characteristic of
the element producing them
Next the figure ==>
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Example: The line spectra of hydrogen

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Spectral Lines of Hydrogen Atom

Spectroscopist studying the spectrum of atomic hydrogen had
identified several series of such lines in different regions of the
electromagnetic spectrum
Three series of spectral lines of atomic hydrogen:

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Rydberg Equation
Rydberg Equation ==> to predict the position and
wavelength of any lines in a given series:

1
1
1
= R 2 2

n2
n1
where is the wavelength of a spectral line, n1 and n2 are
positive integers with n2>n1, and R is the Rydberg constant
(1.096776x107 m-1)
For the visible series of lines, n1=2:

1
1
1
= R 2 2 , withn 2 = 3,4,5,...

n2
2

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The Bohr Model of The Hydrogen Atom

Niels Bohr (1885-1962) suggested a model for the H atom that
predicted the existence of line spectra.
In this model, Bohr used Planck's and Einstein's ideas about quantized
energy and proposed three postulates:
The H atom has only certain allowable energy levels ==> stationary
states. Each of these states is associated with a fixed circular orbit
of the electron around the nucleus
The atom does not radiate energy while in one of its stationary
states. That is, even though it violates the ideas of classical physics,
the atom does not change energy while the electron moves within
an orbit.
The atom changes to another stationary state (the electron moves
to another orbit) only by absorbing or emitting a photon whose
energy equals the difference in energy between the two states:
Ephoton = Estate A Estate B = hv

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Quantum staircase of Hydrogen

Atom

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Bohr's Model
A spectral line results when a photon of specific energy (and
frequency) is emitted as the electron moves from a higher energy
state to a lower one
Therefore, Bohr's model explains that the atomic spectrum is not
continuous because the atom's energy has only certain discrete
levels or states
In Bohr's model, the quantum number n is associated with the
radius of an electron orbit, which is related to the electron's energy
the lower the n value, the smaller the radius of the orbit, and the
lower the energy level
When the electron is in the first orbit (n=1), the orbit closest to the
nucleus, the H atom is in its lowest energy level ==> GROUND
STATE
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Cont'd ....
If the H atom absorbs a photon whose energy equals the
difference between the first and second energy levels, the
electron moves to the second orbit (n=2), the next orbit out from
the nucleus.
When the electron is in the second or any higher orbit, the atom
is said to be in an EXCITED STATE
If the H atom in the first excited state (electron in second orbit)
emits a photon of that same energy, it returns to the ground
state.
When electron drops from an outer orbit to an inner one, the
atom emits a photon of specific energy that give rise to a spectral
line ==> look at the next Figure
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21

Limitations of the Bohr's Model

The Bohr Model failed to predict the spectrum of any other atom,
even that of helium, the next simplest element.
It suitable for H atom and for other one-electron species
But, it does not work for atoms with more than one electron
because in these systems, additional nucleus-electron attractions
and electron-electron repulsions are present
As a picture of the atom, the Bohr model is incorrect, but we still
use the terms ground state and excited state.
and retain one of Bohr's central ideas that: the energy of an
atom occurs in discrete levels

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The Energy States of the Hydrogen Atom

Bohr's work ==> calculation of energy levels of an atom (which
derived from principles of electrostatic attraction and circular
2

Z
motion):
18

E = 2.18x10

J 2
n

where Z is the charge of the nucleus Nuclear Charge

12

18
For H atom with Z=1: E = 2.18x10 J 2 = 2.18x10 18 J 12

n

Therefore, the energy of the ground state (n=1) is:

1
E = 2.18x10 18 J 2 = 2.18x10 18 J
1
The negative sign appears becausewedefine the zero point of the

atom's energy when the electron is completely removed from the

nucleus
Thus, E=0 when n=, so E<0 for any smaller n.
23

Z
18
E = 2.18x10 J 2
n

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 The energy difference between any two levels:

E = E final Einitial = 2.18x10

18

1
1

J
2
n2

final ninitial

We can predict the wavelengths of the spectral lines of H atom:

E = h = hc / = 2.18x10

18

Therefore (nfinal=n2, ninitial = n1):

1
1

J
2
n2

final ninitial

1 2.18x10 18 J 1
1
=
2
2

hc
n
n
final
initial

18
1
2.18x10 J
1

.=
2
34
8
2

6.626x10 J.s 3.00x10 m / s n final ninitial

1
1

. = 1.10x10 m
2
n2

final ninitial
7

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 Energy needed to completely remove the electron from an H atom:

H(g) H+(g) + e- E=?
nfinal= and ninitial=1, and obtain:

1
1
E = E final Einitial = 2.18x10 18 J 2 2
3 1
18
E = 2.18x10 J 0 1 = 2.18x10 kJ / mol

E is positive because energy is absorbed to remove the electron

from the vicinity of the nucleus.
For 1 mol of H atoms:

1kJ
E = 2.18x10 18 J / atom 6.022x10 23 atoms / mol 3
10 J

E = 1.31x10 3 kJ / mol

This is the ionization energy of the H atom, the energy required to form 1
mol of gaseous H+ ions from 1 mol of gaseous H atoms
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de Broglie Wavelength
From E=mc2 and E=hv=hc/ ==> de Broglie: wavelength of any
particles:

= h / mu

Example: Find the de Broglie wavelength of an electron with a

speed of 1.00x106 m/s (electron mass=9.11x10-31 kg; h=6.626x1034 kg.m2/s)

h
6.626x10 34kg.m2 / s
10
=
=
=
7.27x10
m
6
mu 9.11x10 31kg 1.00x10 m / s

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The Heisenberg Uncertainty Principle

Werner Heisenberg (1927) postulated the uncertainty principle.

x.m.u

h
4

x: the uncertainty in position; u: the uncertainty in speed.

Example: An electron moving near an atomic nucleus has a speed
of 6x106 m/s 1%. What is uncertainty in its position (x)?
Solution: Finding uncertainty in speed, u:
u = 1% of u = (0.01)(6x106 m/s) = 6x104 m/s
h
Calculating the uncertainty in position, x:

x.m.u

h
6.626x10 34 kg.m3 / s
9
x

1x10
m
31
4
4mu 4 9.11x10 kg 6x10 m / s

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Summary
Blackbody radiation ==> Planck: Energy is quantized;
only certain values allowed
Photoelectric effect ==> Einstein: Light has particulate
behavior (photons)
Atomic line spectra ==> Bohr: Energy of atoms is
quantized; photon emitted when electron changes
orbit
de Broglie: All matter travels in waves: energy of atom
is quantized due to wave motion of electrons
According to the uncertainty principle, we cannot
know simultaneously the exact position and speed of
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an electron

QUANTUM-MECHANICAL
MODEL OF THE ATOM
GENERAL CHEMISTRY
by Dr. Istadi

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Quantum Mechanics ?
Dual nature of matter and energy
The uncertainty principle
The wave nature of objects on the atomic scale
Quantum Mechanics
Erwin Schrdinger (1926) ==> equation as the basis for the
quantum-mechanical model of the hydrogen atom
The model describes an atom that has certain allowed quantities of
energy due to the allowed wavelike behavior of an electronwhose
exact location is impossible to know

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Atomic Orbital & Probable

Location of Electron
The electron's wave function (, atomic orbital) is mathematical
description of the electron's wavelike behavior in an atom
Schrdinger Equation: H = E
E: energy of atom; : wave function, H: Hamiltonian operator
In complete
form:
2
h d2

d2
d2
2 + 2 + 2 +V x, y, z x, y, z = E x, y, z

2m
dy
dz
8pie dx

Each wave function is associated with one of the atom's allowed energy
states
Each solution to the equation (each energy state of the atom) is associated
with a given wave function ==> Atomic Orbital
In Bohr's model, orbit was an electron's path around the nucleus
Here, orbital is mathematical function with no direct physical meaning
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Electron Probability Density

33

 An electron density diagram and a radial probability

distribution plot show how the electron occupies the space
near the nucleus for a particular energy level.
We cannot know precisely where the electron is at any
moment, but we can describe where it probably is, that is
where it is most likely to be found
Although the wave function (atomic orbital) has no direct
physical meaning, the 2 (probability density) measures
the probability that the electron can be found within a particular
tiny volume of the atom
For a given energy level, we can depict this probability with an
electron probability density diagram or an electron density
diagram
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 Electron density diagram are called electron cloud

The electron moves around the nucleus that would
be appear as a cloud of electron positions.
The electron cloud is an imaginary picture of the
electron changing its position rapidly over time
It does not mean that an electron is a diffuse cloud of
charge
The electron probability density decreases with
distance from the nucleus along a line r.

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Quantum Number of an Atomic Orbital

When the atom absorbs energy, it exists in an excited state and the
region of space occupied by the electron ==> a different atomic
orbital (wave function)
An atomic orbital is specified by three quantum numbers:
Principal Quantum Number (n):
positive integer (1,2,3,...)
Indicates the relative size of the orbital and therefore the
distance from the nucleus of the peak in the radial
probability plot
specifies the energy level of the H atom where the higher
the n value, the higher the energy level.
Example: H atom, when electron ==> n=1 ==> ground state
==> has lower energy; when electron ==> n=2 ==> excited
state ==> has higher energy
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 Angular momentum quantum number (l):

an integer from 0 to n-1
Indicates the shape of the orbital, sometimes called as
orbital-shape quantum number
n limits l
Example: for orbital with n=1 ==> l=0; n=2 ==> l=0,1
Magnetic quantum number (ml):
an integer from -l through 0 to +l
prescribes the orientation of the orbital in the space around
the nucleus, sometimes called as orbital-orientation quantum
number
l sets the possible values of ml.
Example: l=0 ==> ml=0; l=1 ==> ml=-1,0,+1
the number of possible ml values equals the number of
orbitals, which is 2l+1 for a given l value.
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Hierarchy of Quantum Numbers

for Atomic Orbitals

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 The energy states and orbitals of the atom are described with specific
terms and associated with one or more quantum numbers:
1. Level: the atom's energy levels, or shells, are given by the n value
(the smaller the n value, the lower the energy level and the
greater the probability of the electron being closer to the nucleus)
2. Sublevel: the atom's levels contain sublevels, or subshells, which
designate the orbital shape:
l=0 is an s sublevel
l=1 is a p sublevel
l=2 is a d sublevel
l=3 is a f sublevel
s: sharp, p: principal, d: diffuse, f: fundamental
The sublevel with n=2 and l=0 ==> 2s sublevel

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3. Orbital: each allowed combination of n, l, and ml values

specifies one of the atom's orbitals.
Thus the three quantum numbers describes an orbital
expressing its size (energy), shape, and spatial orientation.
Example: from the hierarchy ==> n=2, l=0, and m =0.
l
Example: 3p sublevel has three orbitals:
one with n=3, l=1, and m =-1
l
another with n=3, l=1 and m =0
l
and third with n=3, l=1, and m =+1
l
Give the name, magnetic quantum number, and number of
orbital for the following quantum numbers:

n=3, l=2
n=2, l=0
n=5, l=1
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Shapes of Atomic Orbitals:

s Orbital
The s orbital:
l=0 spherical shape with nucleus at the center s orbital
for H atom's ground state the electron probability density is
highest at the nucleus (Fig. 7.17A)
Fig. 7.17B Because the 2s orbital is larger than the 1s, an
electron in 2s spend more time farther from the nucleus than
when it occupies the 1s.
Fig. 7.17C the highest radial probability is at the greatest
distance from the nucleus
An s orbital has a spherical shape, so it can have only one
orientation and, thus only one value for the magnetic quantum
number: for any s orbital, ml=0
41

Figure 7.17

42

The p Orbital (example: 2p)

43

 An orbital with l=1 has two regions (lobes) of high probability, one
on either side of the nucleus, and is called a p orbital.
In the previous figure, the nucleus lies at the nodal plane of the
dumpbell-shaped orbital.
The maximum value of l is n-1 ==> only levels with n=2 of higher
can have a p orbital.
Therefore, the lowest energy p orbital is the 2p.
Unlike an s orbital, each p orbital does have a specific orientation
in space. The l=1 ==> ml= -1, 0, +1 ==> three mutually
perpendicular p orbitals. They are identical in size, shape and
energy, but differing only in orientation
p orbital associates to x, y, and z axes ==> px, py, and pz
44

The d Orbital (example: 3d)

Radial probability distribution plot

45

46

 An orbital with l=2 is called a d orbital, with 5

possible ml values (-2, -1, 0, +1, +2).
d orbital can have any one of five different
orientations, as depicted in previous figure
The following is one of the seven possible 4f orbitals:

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Orbitals with Higher l Values

Orbitals with l=3 are f orbitals and must have a principal quantum
number at least n=4.
There are seven f orbitals (2l + 1 = 7), each with a complex,
multilobed shape
Orbitals with l=4 are g orbitals, but they will not be discussed,
because they play no known role in chemical bonding

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Energy Levels of the Hydrogen Atom

The energy state of the H atom depends on the principal quantum
number n only.
An electron in an orbital with a higher n value spends its time
farther from the nucleus, so it is higher in energy
Thus, in the case of H atom only, all four n=2 sublevels (one 2s and
three 2p) have the same energy.
and all nine n=3 sublevels (one 3s, three 3p, and five 3d) have the
same energy

LATIHAN SOAL-SOAL

Pages: 285-289

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