Chapter 2.

Atomic Structure

Part I
 Chapter 2. Atomic Structure
Outline
1. Atomic spectra and the Bohr model
2. Quantum mechanics and the electronic structures of hydrogen-like
species
2.1. The wave nature of matter
2.2. Quantum mechanics and atomic structures
2.3. Quantum numbers
2.4. Energy of atomic orbitals
2.5. Shapes of atomic orbitals
3. Polyelectronic atoms (and Electron configuration)
4. Periodic trends in atomic properties
 Suggested Reading and Homework Exercises

• Reading:
 Z&Z, Chapter 2, pp. 53-95.

• Questions/Exercises:

 Z&Z, Chapter 2:
• Review questions: 2, 3, 5, 6, 7, 8, 9
• Questions/exercises: 25, 31, 33, 55, 57, 59, 61, 63, 69, 71, 73,
77, 79, 81, 83, 85, 87, 89, 91, 93, 95, 97, 99, 101, 103, 105,107,
109, 111, 113, 115, 117, 125, 127, 129.

“Z&Z” refers to our adopted textbook by Steven S. Zumdahl, Susan A.

Zumdahl and Donald J. DeCoste, 3rd Ed., 2021.
 1. Atomic Spectra and the Bohr Model
Bohr model was proposed to explain atomic spectra.
Before discussing atomic spectra, let's consider the properties of light.

Light is electromagnetic radiation.

Light has three characteristics:

• Wavelength (l ) – distance
between two peaks or troughs in a
wave.
All electromagnetic radiation:
• Frequency (u ) – number of
waves (cycles) per second that
pass a given point in space

• Speed (c): 2.9979 × 108 m/s 4

The Dual Nature of Light: The Particle Property

Light (electromagnetic radiation) can also be viewed as a stream of

“particles” called photons.

Energy of photons:

Shorter wavelength or Higher frequency  Higher energy

Lower frequency; Higher frequency;
longer wavelength shorter wavelength
5
Classification of Electromagnetic Radiation

6
 Continuous Spectra
When white light or sunlight is passed through a prism, it
produces a continuous (all possible wavelengths and
frequencies) spectrum of colors.

7
 Emission Spectrum of Atoms
An emission spectrum of atoms usually shows a series of
lines, i.e. only certain wavelengths are possible.

8
Emission Spectrum of Hydrogen

R’ = constant
n: 1,2,3…
Z = nuclear charge (1 for H)

9
 The Bohr Model (1)
Z = nucleus charge
• The electron in a hydrogen atom travels around the nucleus
in a circular orbit (shell) -e
Z
• There are many possible orbits (shells). The shells
are distinguished by their distance from the nucleus.

• [n is called the principal quantum number]

• The radii of the orbits are quantized. n2

rn = C
Z
• The velocity of the electron is also quantized. For H, Z =1 o
r(n=1) = 0.52910A
C = constant
 The Bohr Model (2)
• The energy of the electron in an orbit is
quantized and is related by an integer n.
r z2
 Energy of the electron in a shell En = R 2
n=1 n
z2 Z 
2

En = R 2 E n  2.178  1018 J  2  n=2

n n  n =3

where n is the shell number (integer

values of 1, 2, 3….) Energy levels of orbits
Z is the nuclear charge (Z = 1 for H) n=∞
 At n = ∞
n=3
(i.e., electron at infinite distance away)

n=2

 The larger the integer, the more energy an

electron in that orbit has. n=1
Z2
En = R 2
 The farther the electron is from the nucleus the n 11
more energy it has.
Bohr Model and Emission Spectrum of Hydrogen

12
Bohr Model and Emission Spectrum of Hydrogen

• The excited state electron is not very stable.

• It prefers to return to a lower energy state by releasing the
excessive energy in the form of light (or photon).
• The wavelength (λ) of the photon released will have an
energy equal to the energy difference of the two energy
levels in the relaxation process.

light
energy

13
 Bohr Model and Emission Spectrum of
Hydrogen(illustrated in another way)
excited state: higher energy level
Energy levels of atom

n=3
heat

n=2 DE = hu  h(c/l)

n=1
ground state one of excited
states light will be
emmited
ground state: lowest energy level
The energy of light absorbed or emitted is equal to the
difference in the energies of the orbits between which the
electron jumps or falls. 14
Bohr model and Emission Spectrum of hydrogen

R’ = constant
n: 1,2,3…
Z = nuclear charge (1 for H)

15
How can explain the emission spectrum with the Bohr model?
Bohr model and Emission Spectrum of hydrogen

16
Bohr model and Atomic Emission Spectra

R’ = constant; n: 1,2,3…
Z = nuclear charge (1 for H)

DE = h

17
 Exercises
1. According to the Bohr model, as the energy level of
an electron increases, the electron's distance from
the nucleus, on average,
A) increases.
B) decreases.
C) remains the same.
D) cannot be predicted.

18
 Exercises
2. According to the Bohr model, when an electron
moves from the ground state to the excited state, it
A) absorbs energy and moves closer to the nucleus.
B) absorbs energy and moves farther from the
nucleus.
C) emits energy and moves closer to the nucleus.
D) emits energy and moves farther from the nucleus.

19
The Bohr Model of the Atom: Success and Failure

• The Bohr model very accurately predicts the spectrum of

hydrogen.

• However, it had its limitations:

Works only for single-electron atoms. It cannot

explain the atomic spectra of polyelectronic atoms.

Could not account for the intensities or the fine

structure of the spectral lines.

Could not explain the binding of atoms into molecules.

A better theory is needed!!!

20
2. Quantum Mechanics and the Electronic Structures of
Hydrogen-like Species

2.1. The wave behavior of matter

• The quantum mechanical model of atoms is based on the

wave behavior of electrons or atoms.

• Can an electron really behave like a wave?

• Why do we need to describe the motion of electrons in an
atom using the wave property?

• The answers to these questions comes from

• Wave – Particle Duality of Matter
• Heisenberg Uncertainty Principle
21
 Wave – Particle Duality of Matter
Louis de Broglie suggested that if light can behave like matter
(particles) then matter can behave as light.

This concept is called wave – particle duality

particle

wave

v– velocity of particle u– frequency of light

C – speed of light C – speed of light
22
Wave – Particle Duality of Matter: examples

Calculate the wavelength of

(a) a ball (mass = 0.10 kg) traveling at 35 m/s and
(b) an electron (mass = 9.11x10-31 kg) traveling at the
speed of 1.0x107 m/s

23
 Heisenberg Uncertainty Principle
Why do we need to describe the motion of electrons in an
atom using the wave property?

Heisenberg showed that it is impossible to know (or

measure) precisely both the position and velocity (or the
momentum) at the same time.

Dx = uncertainty in position
Dmv = uncertainty in momentum
24
 Heisenberg Uncertainty Principle: Examples

Compare the uncertainty in the positions for the following

cases:
(a) a ball (mass = 1.0 kg) traveling at 100 m/s with an uncertainty
of 1%.
(b) an electron (mass = 9.11x10-31 kg) traveling at the
speed of 5.0x106 m/s with an uncertainty of 1%.

25
2.2. Quantum Mechanics and Atomic Structures

In 1926, Erwin Schrödinger formulated an equation

that describes the wave nature behavior and energies
of atoms

Schrödinger equation:

 = wave function
E = energy

The wave function (Ψ) is related to the probability of finding an

electron in a region of space.
These regions are termed orbitals
26
 Schrö dinger Equation for Hydrogen Atom

The Schrödinger equation can be solved for

hydrogenic (hydrogen-like, single-electron)
Atom or species to give:
Z+ e-
(1) the possible energy states, E

Energies of
atomic orbitals, Hydrogenic atoms:
1 e- only.
(2) corresponding wave functions (or atomic e.g. H, Li2+, Be3+
orbitals), 
 = n, l, ml (r,q,f) Wave functions, or z

atomic orbitals (rqf)

q
• Z = nuclear charge r

• (r,qf) define a point of interest in space y

• n, l, ml: quantum numbers f
x 27
A plot of a Wave function give the shape of an atomic orbital.
 Shapes of s, p and d orbitals
z

s
y
x

pz px py

dxz dyz dxy dx2-y2 dz2

The atomic orbital (electron cloud) defines the region in space

where electrons are most likely to be found. 28
 2.3. Quantum Numbers
General form of wave functions:

 = n, l, ml (r,q,f)

• Quantum Numbers are related to the size, energy, and

shape of the orbitals.

• One set of n, I, ml defines a wave function and therefore

an atomic orbital.

• The relationship among n, l, ml is governed by certain

rules.
29
 Principal Quantum Number (n)

• Determine the energy of the orbital.

– Larger n  Higher energy

• Define the size of orbital.

– Larger n  Larger orbital

• Define the shell.

– We often state that electrons and
orbitals denoted by the same n
values are in the same shell.

• Allowed values: n = 1, 2, 3,….

30
 Angular Momentum Quantum Number (l)
• Define the shape of orbitals
Allowed l values for a given n:
• e.g. s and p orbitals are different in
shape 0, 1, 2, 3……n -1

s p e.g. n = 4; l = 0,1,2,3
l=0 l=1

• Define the sub-shell.

• Discrete sets of orbitals with same l
are called subshell

• Number of subshells within a shell = n

Labels for different l:

l: 0, 1, 2, 3, 4…….
label: s p d f g……
e.g. n = 3, l= 0, 1, 2
labels for atomic orbital 31
 Magnetic Quantum Number (ml)
• Describe the orbital orientations in
space. z
e.g. py and pz are oriented differently

• Allowed values for a given l:

ml = -l, . . . 0, . . . +l x
y

• Number of possible orientation of

orbitals for a given l is 2l+1

pz py

32
2x0+1 2x3+1
Sets of Quantum Numbers for First Four Levels
(Shells) in Hydrogen

Shell Subshell

The number of AOs at each subshell =

The number of AOs at each Level (or Shell ) = 33
 More on Quantum Numbers
• To describe an electron in an atom, we use n, l, ml to
specify the atomic orbital the e- is in.

• e- also has intrinsic spin motion. We use spin

quantum number (ms) to indicate the spin motion.

• Possible value for ms:

1 1
ms = ,
2 2

34
 A Summary on Quantum Numbers
Principal quantum number (n)
n = 1, 2, 3……
 Determine the energy and size of the orbital.
 Define the shell

Angular momentum quantum number (l) define an

For a given n: l = 0, 1, 2, 3,……n – 1 orbital
 Describe the shape and angular dependence of orbital.
 Define the sub-shell.

Magnetic quantum number (ml)

For a given n: ml = -l,…. 0, ……+l
Describe the orbital orientations in space.

Spin quantum number (ms) define spin motion

 ms = ½ , -½
 Indicate the “spin” motion
35
 Exercises
1. How many orbitals are there for the shell with n = 5?
List the quantum numbers.
 Exercises
2. Which of the following sets of quantum numbers
are impossible?

(a) n= 5, I = 5, ml = -2, ms = ½
(b) n = 4, l = 3, ml = 4, ms = - ½
(c) n = 6, l = -1, ml = 0, ms = ½
(d) n = 10000, l = 2, ml = 1, ms =1
(e) All of the above are impossible
 Exercises

3. The magnetic quantum number (ml) is related to

an orbital’s
A) energy B) orientation
C) shape D) size
E) Both A and D
 2.4. Energy of Atomic Orbitals

The energy of an e- in a hydrogen-like atom associated

with a wave function n,l,ml (r, q, f) or atomic orbital is
determined by the equation:
Z2
En = R
n2
Z = charge of nucleus
n = principal quantum number
R = 13.6 ev = 2.178x10-18 J
1
For Hydrogen, z = 1: En = 13.6 (ev)
n2

*Note: Negative sign in this equation!!!

 Graphic Representation

Z2
En = 13.6 (ev)
Conclusion:
n2
(i) Orbital energy is only related to n
(ii) The energy of e- in a hydrogen-like atom is not continuous! This
explains the emission spectrum of hydrogen!!!
 Graphic Representation

shell: a group of orbitals having the same n

subshell: a group of orbitals having the same n and l

 Exercise
1. Which of the following orbitals has a higher energy
for H‒like species?
(a) 3d vs 3p (b) 3d vs 4s (c) 4f vs 5f

42
 2.5 Shapes of Atomic Orbitals

yn, l, ml (r, q, f): Define an atomic orbital (AO).

Atomic orbital: A region in space we can find electron.

Questions:
• How to obtain AOs?
• What do AOs tell us?
• How to represent AOs pictorially? r

• Probability to find an electron at a point?

• Probability to find an electron at a spherical surface?
 2.5.1. General concepts

yn, l, ml (r, q, f): a wave function

Define the shape of an atomic
orbital

y2n, l, ml (r, q, f):

Define the electron density or z
probability to find e- at a
particular point in space (r,qf). (rqf)
(electron density: number of q r
electron per unit volume)
y

f
x
 Radial and Angular Wave Functions
(For reference only)

n, l, ml (r, q, f)
The wave function  n, l, ml (r, q, f) can be factored into:
(a) a radial factor R which is a function of r only and
(b) angular factors Y(q,f) which is a function of q and f.

n, l, ml (r, q, f) = Rn, l, (r) Yl,ml (q,f) (rqf)

q r
Rn,l(r) : Radial wave functions
y

Yl,ml(qf) : Angular wave functions f

x
Some radial wave functions R(r) for hydrogenic atom
Radial Wave Functions
n corresponding
l R(r) orbitals
z
3/2 R 1s
Z
e-Zr/a0
1 2 (rqf)
0
a0 q r

y
1 3/2
2 0 Z Zr f
a0 2 - a e-Zr/2a0 R 2s x
2 2 0

1 3/2
2 1 Z Zr -Zr/2a0 R 2p
2 6 a0 a0 e

2 3/2
3 0 Z 18Zr 2Z2r2 -Zr/3a0 R 3s
27- e
81 3 a0 a0 + 2
a0
4 3/2
3 Z 6Zr Z2r2 R 3p
1 - e-Zr/3a0
81 6 a0 a0
a02
4 3/2
Z Z2r2 R 3d
3 2 e-Zr/3a0
81 30 a0
a02

a0 = 0.529 A 46
(For reference only)
Some angular wave functions Y(qf) for hydrogenic atom Angular Wave Functions
l ml Y(qf) orbitals
1
s
0 0 2 

1 3 cosq
1 0 pz
2 

1 1 3 sinqcosf px
2 

-1 1 3 sinqsinf py
2 
3 0
1 5 3cos2q-1 dz2
4 
z
1
1 15 cosqsinqcosf dxz (rqf)
2 
q r
1 15 cosqsinqsinf
-1 dyz y
2 
f
1 x
2 15 sinqcosf dx2-y2
4 

1 47
-2 15 sinqsinf dxy (For reference only)
4 
 Wave Function, Shape and Meaning of the 1s
Atomic Orbital
Pictorial presentation

R1s
Radial wave function R1s:

Angular wave function Ys: s AO

1s AO
1s = R1sxYs:

2 electron
1s 2= (R1sxYs )2 : density
48
 Another View of the 1s Orbital
Wave function: (1s) = R1sxY1s =

2
Electron density: [ (1s)]2 =

Three representations
of the electron
probability density for
the 1s orbital:

overall 2D-cross section ¼ portion

Other Representations of or or
+
1s orbital:
49
1s Orbital and Electron Density r

How does the electron density change with distance r?

Can be obtained from probability distribution function (R2(r))

(a) The probability distribution for H 1s

orbital in 3D space (presented in cross
section)
2
R1s = R21s =

(b) The probability of finding

electron at points along a line
drawn from the nucleus
outward for H 1s orbital.

50
 1s Orbital and Electron Density
surface area: 4r2
How does the total electron density
of a spherical shell changes with
radius r? e- density at point r: R2
r

total e- density of the surface:

Can be found from 4r2R2(r), the Radial
probability distribution function 4r2R2

Cross section of H 1s Radial probability

orbital probability distribution function 51
 Radial distribution function
4r2R2(r): Radial probability distribution function, indicates the
total electron density of a spherical shell of radius r, or region we
most likely find electron (e-).

surface area: 4r2

e- density at point r: R2
r

total e- density of the surface:

4r2R2

For H, the maximum is at r = 0.529 Å ,

the radius of H.
52
 Exercises
1. Give the name of the listed functions
(a) 

(b) Y(q, f) r

(c) R(r)

(d) R2(r)

(e) 4r2R2(r)

(f) 2
 2.5.2. Shapes of s, p, d and f orbitals
Shapes of s, p and d orbitals
z

s
y
Where do they come from?
x

Why they have different

p
shape?
pz px py

dxz dyz dxy dx2-y2 dz2

Any difference between 1s vs 2s, or 2p vs 3p orbitals?

For polyelectron atoms, 2s and 2p are of different energies. Why?
 The shape of s and p orbitals
Some angular wave functions Y(qf) for hydrogenic atom
l ml Y(qf) orbitals
1 + or or
s
0 0 2 
1 3 cosq
1 0 pz
2 

1 1 3 sinqcosf px
2 

-1 1 3 sinqsinf py
2 

(rqf)
q r

f 55
x
The Boundary Surface Representations of p Orbitals

How many orientations can p orbitals have?

p orbitals, l = 1, ml = -1, 0, 1 (there are three p orbitals)

px py pz
56
 Different Ways of Presenting p Orbitals

y
x
+

pz

py +

57
 Nodal property of p orbitals

Note: p orbitals contain an nodal surface (or plane) or node.

Node: region having zero electron density
z z z

+ y y
y

x - x x

Since such nodes are related to directions (angles), they are termed
58
as angular nodal surface (plane), or simply angular node.
 The Boundary Surfaces of d Orbitals

d orbitals: l = 2, ml = -2, -1, 0, 1, 2 (five d orbitals)

Another representation:
z z z z z

y y y y y

x x x x x
dyz dxy dz2
dxz dx2-y2
59
 Nodes of d Orbitals

d orbitals contain two angular nodal surfaces

(planes).

60
 Nodal surface of dz ??
2

.
Nodes of d Orbitals

62
 Shapes of f Orbitals (reference only)

63
How many angular nodes does a f Orbital has?
Summary: Shapes of s, p and d Orbitals
z

s
y
x

pz px py

dxz dyz dxy dx2-y2 dz2

Very important! You should remember them. 64

 Exercise
1. Sketch the (angular) shapes of py and dyz orbitals.
Indicate the nodes for each orbitals.

py dyz
z

65
 2.5.3. ns, np and nd orbitals
Shapes of s, p and d orbitals
z

s
y
x

pz px py

dxz dyz dxy dx2-y2 dz2

Any difference between 1s vs 2s, or 2p vs 3p orbitals?

 ns Atomic Orbitals

• Generated from RnsxYs

• Ys  s orbital, which has a spherical shape. +

• Rns are different

• Shapes of ns orbitals depend on n.

Examples of Rns (for reference)

R2s:
R1s:
67
 The 1s, 2s, and 3s orbitals
Representations of the electron probability density:

overall 2D-cross section ¼ portion 4r2R2

1s:
Radial Node

2s:

Radial Node

3s:

 Relative sizes:

 Nodal characteristics:

68
Comparisons of 1s, 2s and 3s orbitals
 The 1s, 2s, and 3s orbitals
How would you present 1s, 2s and 3s orbitals with signs?
Electron density
2s 3s
(2ns):
1s

Ys: +

Rns:

AO of ns:
ns =
RnsxYs
1s 70
2s 3s
 np Atomic Orbitals

• Derived from p orbitals.

z z z

y y y

x x x

• As wave functions of np = RnpxYp, the overall shape of

a np orbital will depend on n.

• For p orbitals, l = ___. The smallest n value is ___

71
Electron Density Distribution of 2p and 3p Orbitals

Angular surface node

A 2p orbital:
4r2R2(r),

• Overall it is similar to that of 2p, has an angular node

A 3p orbital:
• But there is also a radial node.

4r2R2(r),
+ - + -

72
Comparison of 2p and 3p Orbitals

 Relative sizes:
 3p is larger than 2p
 3p is more diffused the 2p

 Number nodes:
Both have one angular node
2p has zero, but 3p has one radial node

• We usually use the shape of 2p

orbitals to represent the shape
of any p orbitals.

+ 73
 The 2p and 3p orbitals
How would you present 2p and 3p orbitals with signs?
2p: 3p:

e- density:

Shape of a p orbital:

Number of radial nodes:

Shapes of np
orbitals

74
 nd Atomic Orbitals

• Derived from d orbitals.

z z z z z

y y y y y

x x x x x
dyz dxy dz2
dxz dx2-y2

• As wave functions of nd = RndxYd, the shape of a nd

orbital will also depend on n.

• For d orbitals, l = ___. The smallest n value is ___

• 3d orbitals have the same shapes as d orbitals. 75

Electron Density Distribution
of the d orbitals

76
 Exercise
1. The nodal characteristics of 1s, 2s, 2p, 3s, 3p and 3d are shown blow.

Orbital # of angular nodes # of radial nodes total # of node

1s 0 0 0
2s 0 1 1
2p 1 0 1
3s 0 2 2
3p 1 1 2
3d 2 0 2

Suggest a general formulae relating the number (#) of nodes to quantum

numbers.
Total number of nodes of =

Number of radial nodes =

Number of angular nodes =

 Summary of Electron Density of Orbitals in the
First Three Shells
Density plots (Ψ2)

3s 3p 3d

2s 2p

1s

78
Summary of Quantum Model of H Atom
• In H atom, the electron is in an atomic
orbital.
• An orbital is related to the probability
of finding an electron in a region of
space.
• H has many orbitals. The energy of
the orbitals is quantized (limited to
specific values).
• The energy, shape and orientation of
the orbitals are related to n, l, and ml.
• In the ground state, the e- is in the 1s
orbital.
• The e- can be excited to higher-
energy orbitals if energy is put into the
atom.
79