Lecture Presentation

Chapter 6

Electronic
Structure of Atoms
This chapter is boring!

Xuanjun Zhang
Electronic
University of Macau 2025
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Why do different electromagnetic radiations
exhibit different properties?

Infrared light therapy

紅外線熱療： 促進血液循環

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Electronic Structure
• This chapter is all about electronic
structure—the arrangement and
energy of electrons. 電子排列和能級
• It may seem odd to start by talking
about waves. However, extremely small
particles have properties that can only
be explained in this manner!

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Waves

• The distance between corresponding points

on adjacent waves is the wavelength ().

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Waves 頻率：單位時間内通過某個點的波數
• The number of waves
passing a given point per unit
of time is the frequency ().
• For waves traveling at the
same velocity, the longer the
wavelength, the smaller the
frequency.
• The wavelength in (b) is half
as long as that in (a), and the
frequency of the wave in (b)
is therefore twice as great as
that in (a). Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 • The speed of water waves can vary
depending on how they created.

• In contrast, all electromagnetic radiation

(電磁輻射) travels at the same speed,
namely, the speed of light.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 To understand the electronic structure of
atoms, one must understand the nature of
electromagnetic radiation (電磁輻射).

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Electromagnetic Radiation

無線電頻率

• All electromagnetic radiation travels at the same

velocity: The speed of light (c) is 3.00  108 m/s.
c = 
Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Nature of Energy

Although the wave model of

light explains many aspects
of the behavior of light,
several observations cannot
be resolved by this model:
The wave nature of light does
not explain how an object can
glow (灼熱發光) when its
temperature increases.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Nature of Energy—Quanta

Max Planck explained it

by assuming that energy
comes in packets called
quanta (singular:
quantum 量子).

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Photoelectric Effect 光電子效應
• Einstein (愛因斯坦 ) used
quanta to explain the
photoelectric effect.
• Each metal has a different
energy at which it ejects
electrons. At lower energy,
electrons are not emitted.
• He concluded that energy is
proportional to frequency:
E = h
where h is Planck’s constant,
Electronic
6.626  10−34 J∙s. Structure
of Atoms
© 2015 Pearson Education, Inc.
 Exercise
Calculate and compare energy of a photon
of blue light ( = 450 nm) and red light ( =
620 nm). According to the equation: E = h

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
• Analyze plan  solve  solution
• Calculate and compare energy of a photon of blue light
( = 450 nm) and red light ( = 620 nm).

• E = h (h = 6.62610-34J-s)
• c (speed of light) = 
3.00  108 m/s
•  = c/ = 
= 6.67  1014 s-1

• E(450nm) = (6.62610-34J-s)  (6.67  1014 s-1)

• = 4.42  10-19 J (blue light)
• (Red light 3.21  10-19 J) Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
Three scientists won Nobel Prize in Chemistry 2015 for
the research of “DNA repair”

Tomas Lindahl Paul Modrich Aziz Sancar

https://www.nobelprize.org/prizes/chemistry/2015/summary/

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
"for mechanistic studies of DNA repair“
DNA 修復的細胞機制方面的研究”

Living cells have DNA molecules that carry an organism's genes.

For the organism to live and develop, its DNA cannot change. DNA
molecules are not completely stable, and they can be damaged.
From the mid 1970s, through studies of bacteria, Tomas Lindahl
showed how certain protein molecules, repair enzymes, remove
and replace damaged parts of DNA. In 1989, through studies of
bacterial viruses, Paul Modrich showed how methyl groups
attached to the DNA molecule act as signals for repairing incorrect
replications of DNA. In 1983, through studies of bacteria, Aziz
Sancar showed how certain protein molecules, certain repair
enzymes, repair DNA damaged by ultraviolet (UV) light.
These discoveries have increased our understanding of how the
living cell works, the causes of cancer and aging processes. Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 德國應用化學

Electronic
Structure
of Atoms
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Please compare the energy of a photon of different light:

a: Green > blue

b: UV > blue > red
c: Near-infrared (NIR) > green
d: All photons of different lights have the same energy

Electronic
Structure
of Atoms
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 Atomic Emissions
Another mystery in the early 19th century
involved the emission by atoms and molecules.

霓虹燈Neon Lighting
Plasma等離子體
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Structure
of Atoms
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 Continuous vs. Line Spectra
• For atoms and molecules,
they don’t emit light with
continuous spectrum
(the “rainbow”).

• Only a line spectrum of

discrete wavelengths is
observed. Each element
has a unique line
spectrum.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Bohr Model

Niels Bohr explained these

phenomena in this way:
1. Electrons in an atom can
only occupy certain orbits(軌道)
(corresponding to certain energies).

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Bohr Model
2. Electrons in permitted orbits
have specific, “allowed”
energies(容許能態); these
energies will not be radiated
from the atom.
3. Energy is only absorbed or
emitted in such a way as to
move an electron from one
“allowed” energy state to
another; the energy is defined
by
E = h Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Important Ideas from the
Bohr Model
 Points that are incorporated into the current atomic model
include the following:
1) Electrons exist only in certain discrete
energy levels.
2) Energy is involved in the transition of
an electron from one level to another.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 The Wave Nature of Matter
• Louis de Broglie (路易·德布罗意) theorized that if
light can have material properties, matter should
exhibit wave properties.
• He demonstrated that the relationship between
mass and wavelength was
(h is plank constant; m is mass; v is velocity) 光的波粒二相性
h
 = mv

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Quantum Mechanics
• Erwin Schrödinger(薛定谔)
developed a mathematical
treatment into which both the
wave and particle nature of
matter could be incorporated.
• This is known as quantum
mechanics. (量子力學)
( boring and difficult)

Electronic
Structure
of Atoms
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 Quantum Mechanics
• The solution of Schrödinger’s薛定谔
wave equation is designated with
a lowercase Greek psi ().
• The square of the wave equation,
2, gives the electron density, or
probability of where an electron is
likely to be at any given time.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Quantum Numbers
• Solving the wave equation gives a set of
wave functions 波函數, or orbitals 軌道,
and their corresponding energies.
• Each orbital describes a spatial
distribution of electron density.
• An orbital is described by a set of three
quantum numbers 量子數.

Electronic
Structure
of Atoms
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 Principal Quantum Number (n)
(主量子數)
• The principal quantum number, n,
describes the energy level on which the
orbital resides.
• The values of n are integers ≥ 1.
1, 2, 3, 4…… -
- -

-
neucleon -
-

- -
-
-
- Electronic
- Structure
of Atoms
© 2015 Pearson Education, Inc.
 Angular Momentum Quantum
Number (l) 角量子數
• This quantum number defines the shape of
the orbital.
• Allowed values of l are integers ranging from
0 to n − 1.
• We use letter designations to communicate the different
values of l and, therefore, the shapes and types of orbitals.

Electronic
Structure
of Atoms
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 Angular Momentum Quantum
Number (l) 角量子數

Electronic
Structure
of Atoms
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 s Orbitals 軌道

• The value of l for s orbitals is 0.

• They are spherical in shape.
• The radius of the sphere increases with the
value of n.
Electronic
Structure
of Atoms
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 p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node(節點)
between them.

Electronic
Structure
of Atoms
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 d Orbitals
• The value of l for a
d orbital is 2.
• Four of the five d
orbitals have four
lobes; the other
resembles a p
orbital with a
doughnut around
doughnut the center.

https://www.nobelprize.org/prizes/chemistry/2016/press-release/ Electronic
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 Electronic
Structure
of Atoms
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 f Orbitals

• Very complicated shapes (not shown

in text)
• Seven equivalent orbitals in a sublevel
• l=3

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Magnetic Quantum Number (ml)
磁量子數
• The magnetic quantum number describes the
three-dimensional orientation of the orbital.
• Allowed values of ml are integers ranging
from −l to l:
−l ≤ ml ≤ l
• Therefore, on any given energy level, there
can be up to 1 s orbital, 3 p orbitals, 5 d
orbitals, 7 f orbitals, and so forth.
d orbital: (-2, -1, 0, 1, 2); f orbital: (-3, -2, -1, 0, 1, 2, 3)
Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Magnetic Quantum Number (ml)
• Orbitals with the same value of n form an electron shell.
• Different orbital types within a shell are subshells.

-
- -

-
neucleon -
-

- -
-
-
-
-

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Energies of Orbitals—Hydrogen

• For a one-electron
hydrogen atom, orbitals
on the same shell have
the same energy.
• Chemists call them
degenerate orbitals
(兼併軌道).

For H: 3s, 3p, and 3d have the same energy level Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
Energies of Orbitals—Many-electron Atoms
• As the number of electrons
increases, so does the
repulsion between them.
• Therefore, in atoms with
more than one electron, not
all orbitals on the same shell
are degenerate.
• Orbital sets in the same
sublevel are still degenerate.
• Energy levels start to overlap
in energy (e.g., 4s is lower
in energy than 3d.) Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
Spin Quantum Number, ms 自旋量子数

• In the 1920s, it was discovered that

two electrons in the same orbital do
not have exactly the same energy.
• The “spin” of an electron describes
its magnetic field, which affects its
energy.
• This led to the spin quantum
number自旋量子数, ms.
• The spin quantum number has only
two allowed values, +½ and –½. Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Pauli Exclusion
Principle 不相容原理

• No two electrons in the same atom can have

exactly the same energy.
• Therefore, no two electrons in the same atom
can have identical sets of quantum numbers.
• This means that every electron in an atom must
differ by at least one of the four quantum
number values: n, l, ml, and ms.
Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 5
4p Electron Configurations
• The way electrons are distributed in an atom is
called its electron configuration 電子構型.
• The most stable organization is the lowest
possible energy, called the ground state 基態.

Each component consists of

† a number denoting the energy level;
† a letter denoting the type of orbital;
† a superscript denoting the number of electrons in
those orbitals.
Electronic
Structure
of Atoms
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 Orbital Diagrams
• Each box in the diagram represents one orbital.
• Half-arrows represent the electrons.
• The direction of the arrow represents the
relative spin of the electron.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Hund’s Rule
“For degenerate
orbitals 兼併軌道,
the lowest energy
is attained when the
number of electrons
with the same spin
is maximized.”

 This means that, for a set of orbitals in the same

sublevel, there must be one electron in each orbital
before pairing and the electrons have the same spin,
Electronic
as much as possible. Structure
of Atoms
© 2015 Pearson Education, Inc.
 Chapter Summary and Key Terms

• All of the electromagnetic radiation have the

same velocity 3  108 m/s.

• c = 

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
• An orbital is described by three quantum numbers:

• The principal quantum number, n, (energy level)

• The angular momentum quantum number, l, is indicated
by the letter, s, p, d, f, and so on, corresponding to the
value of 0, 1, 2, 3…..(shape)
• Magnetic quantum number, ml, relates to the orientation
of the orbital in space. For a given value of l, ml can
have integral from –l to l, including 0.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
• An electron shell is the set of all orbitals with the
same value of n, such as 3s, 3p, and 3d
(subshells 的定義).

• There are one orbital in an s subshell, three in a

p subshell, five in a d subshell, and seven in an
f subshell.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Magnetic Quantum Number (ml)
• Orbitals with the same value of n form an electron shell.
• Different orbital types within a shell are subshells.

-
- -

-
neucleon -
-

- -
-
-
-
-

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Exercises in textbook (15th Edition)
• 6.2
• 6.15
• 6.16
• 6.26
• 6.28
• 6.29
• 6.31
• 6.38
• 6.40
• 6.54
Electronic
Structure
of Atoms
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 Spectrum Technology
(included in exam)
1. UV-vis Absorption spectrum (紫外-可見吸收光譜)
2. Fluorescence spectrum (熒光光譜)
3. Infrared absorbance spectrum (紅外吸收光譜)

Electronic
Structure
of Atoms
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 Spectroscopic technique
IR spectrum

• Infrared spectroscopy (IR spectroscopy) is the

spectroscopy that deals with the infrared region of the
electromagnetic spectrum, that is light with a longer
wavelength and lower frequency than visible light.

Electronic
Structure
of Atoms
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• Infrared spectroscopy is based on absorption. As with
all spectroscopic techniques, it can be used to identify
and study chemicals. For a given sample which may be
solid, liquid, or gaseous, the method or technique of
infrared spectroscopy uses an instrument called an
infrared spectrometer (or spectrophotometer) to
produce an infrared spectrum 紅外光譜.

Electronic
Structure
of Atoms
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 Symmetrical Antisymmetrical Scissoring
stretching stretching 剪切振动
对称伸缩振动 非对称伸缩振动

Rocking Wagging Twisting

摇摆的 摇动摆动 扭转的

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
• Infrared (IR) spectroscopy is also very useful for the
quick identification of functional group(s) in a molecule.
Light in the IR wavelength range (700 nm – 1 mm) can
cause molecules to vibrate along bonds. Thus, IR
spectroscopy is most often used technique for
characterization and identification, since the number and
type of chemical bonds gives a specific response.

Carbonyl
Alkene group
group

Electronic
Structure
of Atoms
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 What material?

Sample preparation:
The method we will use is to grind a quantity of the sample with
a specially purified salt (usually potassium bromide KBr) finely
(to remove scattering effects from large crystals). This powder
mixture is then pressed in a mechanical press to form a
translucent ( 半透明的 ) pellet through which the beam of the
spectrometer can pass.

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
• A basic IR spectrum is essentially a graph of infrared light
absorbance (or transmittance) on the vertical axis vs.
frequency or wavelength on the horizontal axis (横轴).
Typical units of frequency used in IR spectra are
reciprocal (倒数) centimeters (called wave numbers), with
the symbol cm−1.
• Units of wavelength: μm, or nanometer (nm), which are
related to wave numbers in a reciprocal way (倒数关系).

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 Convert wavenumber (cm-1) to nanometer
(nm): for example 2000 cm-1

= (reciprocal (倒數) centimeters )

=  
= 5000 nm

Electronic
Structure
of Atoms
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 Applications

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.
 What you should do: Identify the chemical bonds
corresponding to the main absorption peaks

Electronic
Structure
of Atoms
© 2015 Pearson Education, Inc.