Chapter 6

Electronic
Structure of Atoms
Things to Study

• Character of light and photons

• Line spectra and Bohr model
• Character of matter
• Quantum Mechanics and Atomic orbital
• Orbital, Electron configuration, Periodic table

How to understand the elements based on their electron configurations

 Electronic Structure

• This chapter is all about electronic structure—the arrangement and energy

of electrons.

• It may seem odd to start by talking about waves. However, extremely small
particles have properties that can only be explained in this manner!

• Quantum theory explains much of the behavior of electrons in atoms.

Na He
 Waves

• To understand the electronic structure of atoms,

one must understand the nature of electromagnetic radiation.
• The distance between corresponding points on adjacent waves
is the wavelength ().
Waves
• frequency (): The number of waves
passing a given point per unit of time

• The longer the wavelength, the smaller

the frequency.

• If the time associated with the lines to

the left is one second, then the
frequencies would be 2 s–1 and 4 s–1,
respectively.
 Electromagnetic Radiation

• All electromagnetic radiation travels at the same

velocity: The speed of light (c) is 3.00 × 108 m/s.
c = λν
 Electromagnetic Radiation

• There are many types of electromagnetic radiation.

• They have different wavelengths and energies from each other.
• The typical wavelength unit used vary based on the lengths.
Q
The yellow light given off by a sodium vapor lamp used for public lighting has a
wavelength of 589 nm. What is the frequency of this radiation?

c = λν

ν = c/ λ 𝟑. 𝟎𝟎 × 𝟏𝟎𝟖 𝒎/𝒔 𝟑. 𝟎𝟎 × 𝟏𝟎𝟖 𝒎/𝒔

= =
𝟓𝟖𝟗 𝒏𝒎 𝟓𝟖𝟗 × 𝟏𝟎−𝟗 𝒎

= 𝟓. 𝟎𝟗 × 𝟏𝟎𝟏𝟒 /𝒔

c = λν λ= c/ν ν = λ/c
 Electronic Properties NOT
Explained by Waves

White light, A laser, which consists of just a

a combination of the colors single wavelength, a result of a
of the visible spectrum quantized process

• Three observed properties associated with how atoms interact with

electromagnetic radiation can NOT be explained by waves:
1) the emission of light from hot objects (blackbody radiation)
2) the emission of electrons from metal surfaces on which light shines
(the photoelectric effect)
1) the emission of light from electronically excited gas atoms (emission spectra)
 Hot Objects and the Quantization of Energy
What is the relationship
between the temperature
and the emitted raditation? • The wave nature of light does not explain
how an object can glow when its
temperature increases.
• Energy can be either released or absorbed
by atoms only in discrete “chunks” of some
minimum size. Max Planck (1858–1947)

Quantum (meaning “fixed amount”)

The color and intensity of the
light emitted by a hot object, the smallest quantity of energy emitted or
such as this nail, depend on absorbed as electromagnetic radiation.
the temperature of the object
The Nature of Energy—Quanta

Max Planck explained it by assuming that

energy comes in packets called quanta
(singular: quantum).

Matter can emit and absorb energy only in

whole number multiples of hν, such as 1 hν,
2 hν, 3 hν,

E = hν
h : Planck constant, 6.626 * 10 - 34 J.s
1918 Nobel Prize in Physics for his work on quantum theory
Radiation of frequency ν = E/h can be generated only when enough E is acquired.
 The Photoelectric Effect

• Einstein 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)
• the radiant energy striking the metal surface behaves like a stream of tiny energy pack
: “particle” of energy, a photon. (quanta, Marc Flank)
• He concluded that energy is proportional to frequency:
h is Planck’s constant, 6.626 × 10−34 J∙s.
Q
The yellow light given off by a sodium vapor lamp used for public lighting
has a wavelength of 589 nm. What is the Energy of this radiation?

E = hν (h, 6.626 × 10−34 J∙s)

= (𝟔. 𝟔𝟐𝟔 𝒙 𝟏𝟎−𝟑𝟒 J∙s) ( 𝟓. 𝟎𝟗𝟑 𝒙 𝟏𝟎𝟏𝟒 /𝒔)

= 𝟑. 𝟑𝟕 𝒙 𝟏𝟎−𝟏𝟗 J
 Atomic Emissions (line spectra)
Another mystery in the early twentieth century involved the emission spectra
observed from energy emitted by atoms and molecules.
How line spectra relate to the idea of quantized energy states of electrons in atoms?

Atomic emission of H and Ne.

Different gases emit light of different
characteristic colors when an electric current
is passed through them.
*Monochromatic Radiation
: composed of a single wavelength

*Polychromatic Radiation
: composed of many different wavelength

*Spectrum
: Polychromatic radiation is separated into its component radiations
 Continuous vs. Line Spectra

• For atoms and molecules, one does not

observe a continuous spectrum, as
one gets from a white light source.

• Only a line spectrum of discrete

wavelengths is observed.

• Each element has a unique line

spectrum.
 The Hydrogen Spectrum

• Hydrogen : 410 nm (violet), 434 nm (blue), 486 nm

(blue-green), and 656 nm (red)
• Johann Balmer (1885) discovered a simple
formula relating the four lines to integers.
• Johannes Rydberg advanced this formula. λ: the wavelength of a spectral line
RH : the Rydberg constant
• Neils Bohr explained why this 1.096776 * 107 /m
mathematical relationship works.
n1 < n2 : positive integers
The Bohr Model

• Niels Bohr adopted Planck’s

assumption and explained
these phenomena in this
way:
1) Only orbits of certain radii,
corresponding to specific
energies, are permitted for
the electron in a hydrogen
atom.
The Bohr Model
2) An electron in a permitted
orbit is in an “allowed” energy
state. An electron in an
allowed energy state does
not radiate energy, and,
therefore, does not spiral into
the nucleus.

2) Energy is emitted or
absorbed by the electron only
as the electron changes from
one energy state to another.
This energy is is emitter of
absorbed as a photon that
has energy E = h.
 The Bohr Model

• Electrons in the lowest energy state are in the ground state.

• Any energy higher is called an excited state.
• Since each orbit has a specific value compared to RH,
transitions from one energy level to another can be calculated:
Calculate the energy of an electron that has a +Z positive charge and an electron
that has a Coulomb interaction and moves in a circle around the nucleus.

( ) Z2

H: Z→ 1

me: mass of e, 9.109390× 10-31 kg

e: charge of e, 1.6021773× 10-19 C
h: 6.62608× 10-34 J · s
ε0: vacumn permittivity, 8.854× 10-12 C2/J · m
mee4/8h2ε02 = 2.180× 10-18 J = 1 rydberg

Z2
Values of Transitions

• What do the values mean using the Bohr Model?

• A positive ΔE means energy is absorbed. A

photon is absorbed in this instance.
This happens if nf > ni.

• A negative ΔE means energy is released. A

photon is emitted in this instance.
This happens if nf < ni.
 Limitations of the Bohr Model

• It only works for hydrogen!

• Classical physics would result in an electron falling into the positively
charged nucleus. Bohr simply assumed it would not!
• Circular motion is not wave-like in nature.

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, which are described by
quantum numbers.
2) Energy is involved in the transition of an electron from one level to another.
 If an electron makes a transition from the ni = 4 level to a lower-energy level, nf = 3, 2, or 1, which
transition would produce a photon with the shortest wavelength?

E = h = hc/λ ni = 4 → nf = 1
What are the energy and wavelength of such a photon, and in which region of the electromagnetic
spectrum does it lie?
Diffraction ⇒ Wave Photoelectric effect ⇒ Particle

Wave-particle duality of electromagnetic radiation

Does matters also have wave-like properties?

Wave-particle duality of matters?
 The Wave Nature of Matter

• Louis de Broglie
“If light can have material
properties, matter should exhibit
wave properties!”

• Louis de Broglie demonstrated

that the relationship between
mass and wavelength was:

Electron micrograph h
→The wave nature of light λ = mv
 hc
E= λ

hc
λ= E

E = mc2

h
λ = mc

h
λ = mv
What is the wavelength of an electron moving with a speed of 5.97 × 106 m/s?
The mass of the electron is 9.11 × 10–31 kg.
(h = 6.626 × 10–34 J-s)

(6.626 𝑥 10−34 𝐽∙𝑠) 1 𝑘𝑔∙𝑚2/𝑠2

= −31 6 𝑚 ( )
(9.11 𝑥 10 𝑘𝑔)(5.97 𝑥 10 ) 1 𝐽
𝑠

= 1.21 𝑥10−10 𝑚 = 0.122 𝑛𝑚

 The Uncertainty Principle

Heisenberg showed that the

more precisely the momentum of
a particle is known, the less
precisely its position is known:

h
(Δx) (Δmv) 
4π

Werner Heisenberg
 h
(Δx) (Δmv) 
4π
Electron
: 9.11 x 10-31 kg, 5 x106 m/s

If 1% uncertainty of velocity ∆𝑣 = 0.01 × (5 𝑥 106 m/s)

ℎ −34 1 𝑘𝑔 ∙ 𝑚 2/𝑠2
∆𝑥 ≥ = 6.626 × 10 𝐽 ∙ ℎ × ( )
4𝜋𝑚∆𝒗 1 𝐽
4𝜋 (9.11 × 10−31 𝑘𝑔)(5 × 104 𝑚)
= 1 × 10−9

∗∗ 𝑑𝑖𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚 ≈ 1 𝑥 10−10

 Quantum Mechanics

• Erwin Schrödinger developed a mathematical treatment

into which both the wave and particle nature of matter
could be incorporated.
• The solution of Schrödinger’s wave equation for
hydrogen yields wave functions for the electron.
• The square of the wave function gives the electron
density, or probability of where an electron is likely to
be at any given time.
• Solving the wave equation gives a set of wave
functions, or orbitals, and their corresponding
energies.
• Each orbital describes a spatial distribution of electron
density.
• An orbital is described by a set of three quantum
numbers.
 Quantum Numbers

Wave equation
gives a set of wave functions, or
orbitals, and their corresponding energies.

Orbitals
spatial distribution of electron density.
described by a set of three quantum numbers.
The probability of finding the particle in a region is proportional to the value of Y2.

A particle has zero probability density wherever the wavefunctions has nodes.
출처: 생명의 화학, 삶의 화학
 Principal Quantum Number (n)

• The principal quantum number, n,

describes the energy level on which the orbital resides.

• The values of n are integers ≥ 1. (1,2,3,…)

• These correspond to the values in the Bohr model.

 Angular Momentum Quantum Number (l)

• This quantum number defines the shape of the orbital.

• Allowed values of l are integers ranging from 0 to (n − 1)
 Magnetic Quantum Number (ml)

• 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.
n energy level 2

l shape of the orbital 0,1

s,p

ml three-dimensional orientation of the orbital

0,1

0 -1, 0, 1
 Quantum Numbers
• Orbitals with the same value of n form an electron shell.
• Different orbital types within a shell are subshells.
 s Orbitals

• 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.
s Orbitals
• For an ns orbital, the number
of peaks is n.

• For an ns orbital, the number

of nodes (where there is zero
probability of finding an
electron) is n – 1.

• As n increases, the electron

density is more spread out
and there is a greater
probability of finding an
electron further from the
nucleus.
 p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.
 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 the center.
 f Orbitals
• Very complicated shapes
• Seven equivalent orbitals in a sublevel
• l=3
Energies of Orbitals—Hydrogen

• For a one-electron hydrogen

atom, orbitals on the same
energy level have the same
energy.

• Chemists call them degenerate

orbitals.
 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 energy level 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.)
 Spin Quantum Number, ms

• 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, ms.

• The spin quantum number has only two

allowed values, +½ and –½ .
 Pauli Exclusion Principle

• No two electrons in the same atom can have the

same set of four quantum numbers.

• Therefore, no two electrons in the same atom can

have the exact same energy.

• 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.
 Electron Configurations
• The way electrons are distributed in an atom is called its electron
configuration.
• The most stable organization is the lowest possible energy, called the
ground state.
• 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.

4p 5
 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.
 Hund’s Rule
“When filling degenerate orbitals the lowest energy is attained when the number of electrons
having the same spin is maximized.”
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, as much as possible.
Condensed Electron Configurations
2
He
• Elements in the same group of the periodic table have
1s2 the same number of electrons in the outer most shell.
10
Ne These are the valence electrons.
2s22p6

18 • The filled inner shell electrons are called core

Ar
3s23p6
electrons. These include completely filled d or f
sublevels.
• We write a shortened version of an electron
configuration using brackets around a noble gas symbol
and listing only valence electrons.

Cl: [Ne]3s2 3p5

 Transition Metals

• Argon (atomic number 18)

ends period 3. Its electron
configuration is
1s22s22p63s23p6.
• Potassium (atomic number
19) might be expected to
have electrons in 3d. BUT 4s
fills next.
• Transition metals follow the
filling of 4s by filling 3d in the
4th period.
 Lanthanides and Actinides
• The elements which fill the f orbitals have special names as a portion of
a period, not as a group.
• The lanthanide elements (atomic numbers 57 to 70) have electrons
entering the 4f sublevel.
• The actinide elements (including Uranium, at. no. 92, and Plutonium,
at. no. 94) have electrons entering the 5f sublevel.
 Periodic Table
• We fill orbitals in increasing order of energy.
• Different blocks on the periodic table correspond to different types of orbitals: s =
blue, p = pink (s and p are representative elements); d = orange (transition
elements); f = tan (lanthanides and actinides, or inner transition elements)
• The s and p blocks are called the main-group elements.
 Some Anomalies
• Some irregularities occur when there are enough electrons to half-fill s and d orbitals
on a given row.
 Chromium as an Anomaly

• For instance, the electron configuration for chromium is

[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.
• This occurs because the 4s and 3d orbitals are very close in energy.
• These anomalies occur in f-block atoms with f and d orbitals, as well.
Boron, atomic number 5, occurs naturally as two isotopes, 10B and 11B, with natural abundances of 19.9% and
80.1%, respectively.
(a) In what ways do the two isotopes differ from each other? Does the electronic configuration of 10B differ from
that of 11B?
(b) Draw the orbital diagram for an atom of 11B.
(c) Which electrons are the valence electrons?
(d) Indicate three ways in which the 1s electrons in boron differ from its 2s electrons.
(e) Elemental boron reacts with fluorine to form BF3, a gas. Write a balanced chemical equation for the reaction
of solid boron with fluorine gas.
(f) (e) ∆Hf for BF31g2 is -1135.6 kJ>mol.
(g) Calculate the standard enthalpy change in the reaction of boron with fluorine.