CHEM 1020:

General Chemistry-I
Professor Haipeng Lu (呂海鵬)

Department of Chemistry
The Hong Kong University of Science and Technology
Spring 2023
Chem-1020: Lecture 3

• In last chapter, we have

➢introduced matters and classification, elements, compounds, periodic table, atoms, three
fundamental chemistry laws
➢Introduce the 1st, 2nd, and 3rd atomic model
➢ 1st model: Dalton (atoms are indivisible and indestructible; don’t know what is inside of atoms) 1808
o Discovery of electron 1887
➢ 2nd model: Thompson (Plumb Pudding model; fail to explain Rutherford’s experiments) 1904
o Discovery of nucleus 1909
➢ 3rd model: Rutherford (Nuclear model) 1911
Fail to explain the absorption/emission spectrum of hydrogen

• In chapter 2, we will
• Introduce the 4th (Bohr model) and 5th (Quantum mechanic model) of atomic structure
and periodicity

2
Chapter 2. Atomic Structure

Part I

3
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

4
 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.
5
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 – the wave property.

Light has three characteristics:

• Wavelength (l ) – distance between two peaks or

troughs in a wave.

• Frequency (u ) – number of waves (cycles) per second

that pass a given point in space c
ν=
• Speed (c): 2.9979 × 108 m/s λ

6
The nature of waves

c
ν=
λ
➢ How many cycles per second

Shorter wavelength → Higher frequency Can you calculate their wavelength?

7
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:

hc
Ephoton = h = h = 6.626 x10-34 J s (Planck’s constant)
λ v = frequency (Hz)

Shorter wavelength or Higher frequency  Higher energy

Lower frequency; Higher frequency;
longer wavelength shorter wavelength

8
Classification of Electromagnetic Radiation

9
 Continuous Spectra

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

10
 Absorption Spectrum of Atoms

• Let a white light to pass through H2 gas, the regions being absorbed by H2 will
become black.

H2 gas

• An absorption emission spectrum of atoms usually shows a series of lines, i.e. only
certain wavelengths are possible.

11
Emission Spectrum of Atoms

An emission spectrum of atoms also shows a series of lines, i.e. only certain
wavelengths are possible.

What does it mean and Why? 12

Absorption and emission process
high
Energy • Imagine there are some virtual excited states that
atoms can be pumped to

• The absorption process (low E to high E) is when

ground state is excited to excited states through
the absorption of photons (hv)

excited states • The emissiong process (high E to low E) is when

Excitation the excited states are relaxed back to ground state,
(higher energy)
(absorption) and is associated with emission of photos (hv)
Relaxation
(emission)

hv • The fact that the absorption and emission spectra

hv are discontinuous means that there are only
certain, discrete excited states, or in other words,
quantized electronic states
Ground state
(lowest energy) low

13
The Bohr Model (1)
Z = nucleus charge
• The electron in a hydrogen atom travels around the nucleus in a -e
circular orbit (shell)
Z
• There are many possible orbits (shells). The shells are
distinguished by their distance from the nucleus.

• n is the shell number, called the principal quantum number 𝑛2

• n is integer, n=1, 2, 3, 4… rn = C
𝑍
n = 1, 2, 3, 4,
• The radii of the orbits are quantized. …
𝑛2
rn = C o As n is integer, rn is quantized
𝑍
o For H, Z = 1, r(n=1) = 0.529 Å
C = constant=0.529 Å

• The velocity of the electron is also quantized (as it is also related to n).

14
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 n=2 Higher E
En = R 2 R is a constant, R = 2.178 x 10-18 J
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=∞
𝑧2
 At n = ∞, E = ─R =0 (i.e., electron at infinite distance away)
∞ n=3
𝑧2
 At n ≠ ∞, E = ─R 2
= a negative value, meaning the energy is
𝑛
lower than infinite distance n=2

 The larger the integer (n), the more energy an electron in that
orbit has. n=1
Z2
 The farther the electron is from the nucleus the more energy it En = R 2
n
has. 15
Bohr Model and Emission Spectrum of Hydrogen

𝑧2
• Because the shell energies are quantized (E = ─R 2 ) ,the transitions between different
𝑛
shells (e.g., from n1 to n2) will ONLY contain certain energy, as
1 1
∆E = E1 ─ E2 = ─ 𝑅 ∗ 𝑍2 ∗ ( 2 − )
𝑛1 𝑛22
16
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.

1 1 light
∆E = E1 ─ E2 = ─ 𝑅 ∗ 𝑍2 ∗ ( 2 − 2) energy
𝑛1 𝑛2

17
Bohr Model and Emission Spectrum of Hydrogen

excited state: higher energy level

Energy levels of atom

n=3
excite
heat

n=2 DE = hu = h(c/l)
1 1
= ─ 𝑅 ∗ 𝑍2 ∗ ( − )
𝑛12 𝑛22
n=1
ground state one of excited
states light will be
emmited
ground state: lowest energy level R is a constant, R = 2.178 x 10-18 J

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.
18
Bohr Model and Emission Spectrum of Hydrogen

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

• Bohr’s model explains the experimental emission spectrum of hydrogen

19
Bohr Model and Emission Spectrum of Hydrogen: Excise

• When the hydrogen atom returns to its lowest possible energy state, it is
called the ground state
• When the electron falls from n=6 to n=1, ΔE can be computed by:
ΔE = energy of final state − energy of initial state −18  Z2 
E = −2.178×10 J 2 
= E1 − E6 = ( − 2.178×10−18 J ) − ( − 6.050×10 −20 J ) n 

= − 2.117×10−18 J

• The negative sign indicates that the atom has lost energy and is in a more
stable state

20
Bohr Model and Emission Spectrum of Hydrogen: Excise

• The energy lost is taken away from the atom by the emission of a photon
whose wavelength can be calculated from:
c hc
ΔE = h   or λ =
 λ ΔE

• ΔE, the change in energy of the atom, is equal to the energy of the emitted
photon

hc (6.626×10 −34 J . s )(2.9979×10 8 m / s ) −8

λ= = −18
= 9.383×10 m
ΔE 2.117×10 J
Is it visible?

21
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.

22
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.

23
Exercises

• Calculate the energy required to excite the hydrogen electron from level n =
1 to level n = 2. Also calculate the wavelength of light that must be absorbed
by a hydrogen atom in its ground state to reach this excited state.

• Solution
 Z2 
• Using the equation E = −2.178×10 −18
J 2  with Z = 1, we have:
n 

−18  12 
E1 = −2.178×10 J  2  = −2.178×10−18 J
1 
−18  12 
E2 = −2.178×10 J  2  = −5.445×10−19 J
2 
c hc
ΔE = h   or λ =
 λ ΔE
24
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.

If electron (-) and nucleus (+) only has columbic interaction, why don’t electrons
just fall into the nucleus?

A better theory is needed!!!

25
Four models of atomic structures so far…

26
2. The 5th model of atomic structure: Quantum Mechanic model

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

27
 2. The 5th model of atomic structure: Quantum Mechanic model

Four fundamental aspects of Quantum mechanical model of atomic structure:

➢ Electrons, like all other particles with rest masses, display wave behaviors;
(λ= h/p; ν = E/h; de Broglie hypothesis, 1924)

➢ There exists an intrinsic and fundamental limit to the precision with which certain
pairs of physical properties of a particle, such as position x and momentum p, can
be known (or measured) simultaneously;
(∆x. ∆ p≥ 𝒉/𝟒𝝅; Heisenberg uncertainty principle, 1927 )

➢ The motion of electron is described by wave-functions (called atomic orbitals), and

governed by the Schrodinger equation; Each and every atomic orbital has a
characteristic energy associated with it (called the energy of atomic orbital);
෡
( 𝑯ψ(x,y,z) =E ψ(x,y,z) ; Schrodinger equation, 1926 )

➢ The atomic orbital, when squared, describes the probability of finding the electron
at a spatial location; Therefore, an atomic orbital is simply the probability
amplitude function. ( | ψ(x,y,z) |2; Born’s rule, 1926 )

28
Wave – Particle Duality of Matter
Louis de Broglie suggested that if light can behave like matter (particles), then any matter can
behave as light (wave). (this was a bold idea)

This concept is called wave – particle duality

For light frequency

hc
wave Ephoton = h = u– frequency of light
λ
C – speed of light
particle

For any matter

Replace c with v
velocity v– velocity of particle
λ- wavelength of particle
29
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

ℎ
λ=
𝑚𝑣
6.626 × 10−34
=
𝑚𝑣

= 1.9 x 10−34 m (ball)

= 7.3 x 10−11 m (electron)

30
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
31
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%.

ℎ
∆𝑥∆ 𝑚𝑣 ≥
4𝜋
ℎ
∆𝑥 ≥ / ∆ 𝑚𝑣
4𝜋

(a) For a ball: ∆ 𝑚𝑣 = 1.0 x 100 x 0.01 = 1 kg m/s

➢ ∆𝑥 ≥ 6.626 × 10−34 /(4 𝜋) / 1 = 0.527 × 10−34 m (extremely small…)

(b) For an electron: ∆ 𝑚𝑣 = 9.11x10-31 x 5.0 x 106 x 0.01 = 4.6 x 10-26 kg m/s
➢ ∆𝑥 ≥ 6.626 × 10−34 /(4 𝜋) / (4.6 x 10-26 ) = 1.1 × 10−9 m (comparable with size of atom (10-10 m)!!)

➢ In other words, we do not know where electrons are precisely! (so Bohr model is incorrect!)
➢ If you don’t know where they are, how can you describe them?
32
2.2. Quantum Mechanics and Atomic Structures
• In 1926, Erwin Schrödinger formulated an equation based on Standing
Waves that describes the wave nature behavior and energies of atoms.
– Standing waves are stationary waves that do not travel along any length
– Only certain orbits have a circumference into which whole number wavelengths of
standing electron waves will fit
– Other waves produce destructive interference of the standing electron wave
– we can only know where electrons are by chance (possibility), which is square of ψ,
| ψ(x,y,z) |2

add boundary conditions,

reflected back
Standing wave
Transverse wave
(blue wave = red + green)
The sum of two counter-propagating waves (of equal amplitude and frequency) creates a standing wave. (for reference)
33
2.2. Quantum Mechanics and Atomic Structures
• In 1926, Erwin Schrödinger formulated an equation based on Standing
Waves that describes the wave nature behavior and energies of atoms.
– Standing waves are stationary waves that do not travel along any length
– Only certain orbits have a circumference into which whole number wavelengths of
standing electron waves will fit
– Other waves produce destructive interference of the standing electron wave
– we can only know where electrons are by chance (possibility), which is square of ψ,
| ψ(x,y,z) |2

Schrödinger equation:
H: operator (partial differential)
 = 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
34
What you need to know about Schrödinger equation

• The solutions to the Schrodinger equation bring forth (generate) atomic orbitals (including their shapes) and
their quantized energies.

• Therefore, in order to answer such questions as

➢ how are atomic orbitals obtained?
➢ how to understand the physical meaning of atomic orbitals?
operator energy
➢ how to represent atomic orbitals?
➢ how are atomic orbitals different from the circular orbits in Bohr model?
➢ What are the limitations of atomic orbitals from QM model?

• It is inevitable to “invoke” Schrodinger equation in this section. However, the mathematics mentioned in this
section, including all the math functions for atomic orbitals are NOT required! After this section, please
➢ Ignore all the math for atomic orbital!
➢ Focus only on the graphic and (quantum) number representation of atomic orbitals!

35
 What you will get by solving the Schrödinger equation

• Ok, after you “solved” Schrodinger equation for hydrogenic (hydrogen-like, single-electron) atom,
you will obtain the following two things:
• Energies (E) of orbitals Hydrogenic atoms:
1 e- only.
• Expression of ψ (wave function), which describes atomic orbitals e.g. H, Li2+, Be3+

E = energy

Some math…
 = wave function expression
operator energy

• Let’s skip the math and go to the solutions directly…

36
 Solution of Schrödinger Equation for Hydrogen Atom

(1) the possible energy states, E

z2 Energies of Note: this is exactly the same as the Bohr model (as it should),
En = R 2 atomic orbitals indicating quantized energy states
n
Recall that n is the principal quantum number
z is the nuclear charge; R is a constant
(2) corresponding wave functions (or atomic orbitals), ψ
z

Wave functions, or
 = n, l, ml (r,q,f) q
(rqf)
atomic orbitals r

• Ψ is a function of r (radius), q and f f

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

• n, l, ml: quantum numbers r: how far it is from nucleus

(the distance)
A plot of a Wave function thus give the shape of an atomic orbital. q and f: what angles it is
(the coordinates)
37
2.3. Quantum Numbers

General form of wave functions:

z2
 = n, l, ml (r,q,f) = Rn,l (r) Yl,ml (qf) = Rn,l (r) Pl,ml (q) Fml (f) En = R 2
n
Radial factor angular factor

• n: principal quantum number

• Introduced when solving Rn,l (r), related with the distance r (e and nucleus)
• l: angular momentum quantum number
• Introduced when solving Pl,ml (q), related with coordinate q and therefore shapes
• ml: magnetic quantum number
• Introduced when solving Fml(f), related with coordinate f and therefore orientations

• 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.
38
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,…. (integer)

z2
En = R 2
n

39
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 40
40
Magnetic Quantum Number (ml)

• Describe the orbital orientations in space.

e.g. py and pz are oriented differently z

• Allowed values for a given l:

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

• Number of possible orientation of orbitals for

a given l is 2l+1

pz py
How is px?
2x0+1 2x3+1
41
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 ) =
42
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

43
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)

➢For a given n: l = 0, 1, 2, 3,……n – 1
➢ Describe the shape and angular dependence of orbital.
define an 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

44
 Exercises
1. How many orbitals are there for the shell with n = 5?
List the quantum numbers.
• n = 5, possible l values are
l = 0, 1, 2, 3, 4 (corresponding to s, p, d, f, g subshells)

• Each subshell has the number of atomic orbitals (AOs) = 2 l +1

• So, we have # of AOs:
• 2*0+1=1
• 2*1+1=3
• 2*2+1=5
• 2*3+1=7
• 2*4+1=9

• In total we have: 1+3+5+7+9 = 25 45 (also = n2)

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

46 E
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

47 B
 Solving the Schrödinger equation will give you

• Solving Schrodinger equation for hydrogenic (hydrogen-like, single-electron) atom will obtain the
following two things:
• Energies (E) of orbitals Hydrogenic atoms:
1 e- only.
• Expression of ψ (wave function), which describes atomic orbitals e.g. H, Li2+, Be3+

E = energy

Some math…
 = wave function expression

• Below we will look into more details of Energy (E) and Wave function (ψ)

48
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 (ev)
For Hydrogen, z = 1: En = 13.6
n2

*Note: Negative sign in this equation!!!

49
Graphic Representation

Energy

Z2
En = 13.6 (ev)
Conclusion:
n2
(i) Orbital energy is only related to n (and not related to ml) for hydrogen-like atoms
(ii) The energy of e- in a hydrogen-like atom is not continuous! This explains the emission
spectrum of hydrogen!!! 50
Graphic Representation

shell: a group of orbitals having the same n

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

51
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

52
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:
r

• How to obtain AOs?

• What do AOs tell us?
• How to represent AOs pictorially? (how do you know they look like that?)
• Probability to find an electron at a point?
• Probability to find an electron at a spherical surface?
53
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 probability to find e- at a z
particular point in space (r,qf).
(electron density: number of electron per unit volume) (rqf)
q r

f
x
Intensity indicates probability

54
Radial and Angular Wave Functions (For reference only)

n, l, ml (r, q, f) (rqf)

q r

The wave function  n, l, ml (r, q, f) can be factored into: y

(a) a radial factor R (r) which is a function of r only and f
(b) angular factors Y(q,f) which is a function of q and f. x

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

Rn,l(r) : Radial wave functions

Yl,ml(qf) : Angular wave functions

55
Radial Wave Functions: R(r)

Some radial wave functions R(r) for hydrogenic atom z

n corresponding (rqf)
l R(r) orbitals
q r
3/2 R 1s
1 0 2 Z e-Zr/a0
a0 y
3/2
2 0 1 Z Zr f
a0 2- e-Zr/2a0 R 2s
x
2 2 a0

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

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 a0 e-Zr/3a0
81 30 a02

a0 = 0.529 A
56
(For reference only)
Angular Wave Functions Yl,ml (q,f)

Some angular wave functions Y(qf) for hydrogenic atom

z
l ml Y(qf) orbitals
1 (rqf)
s
0 0 2  q r
1 3
1 0 cosq pz
2  y
1
1 3 sinqcosf px f
2 
x
-1 1 3 sinqsinf py
2 
3 0
1 5 3cos2q-1 dz2
4 
1 1 15 cosqsinqcosf dxz
2 

1 15 cosqsinqsinf
-1 dyz
2 

1 15 sinqcosf
2 dx2-y2
4 

1 15 sinqsinf
-2 dxy
4 

(For reference only)

57
Wave Function, Shape and Meaning of the 1s Atomic Orbital

𝑍
Radial wave function R1s: 2( )3/2 𝑒 −𝑍𝑟/𝑎0 R1s
𝑎0

1
Angular wave function Ys: s AO constant
2 𝜋

1s AO constant
𝑍 3/2 −𝑍𝑟/𝑎 1
1s = R1sxYs: 2( ) 𝑒
𝑎0
0
2 𝜋

2 electron
𝑍 1
1s 2 = (R1sxYs)2: 2( )3/2 𝑒 −𝑍𝑟/𝑎0
𝑎0
density
2 𝜋

58
 Another View of the 1s Orbital
𝑍 3/2 −𝑍𝑟/𝑎 1 Independent of q and f.
Wave function: (1s) = R1s×Y1s = 2( ) 𝑒 0
𝑎0 2 𝜋 Meaning: isotropic/spherical!!

𝑍 3/2 −𝑍𝑟/𝑎 1 2 The larger the r, the

Electron density: [ (1s)]2 = 2( ) 𝑒
𝑎0
0
2 𝜋 smaller the probability of
finding electrons!
Intensity decreases at larger r
To visualize:
Three representations of the
electron probability density for the
1s orbital:

overall 2D-cross section ¼ portion

Other Representations of 1s orbital: or + or

59
1s Orbital and Electron Density
How does the electron density change with distance r?
Intensity decreases at larger 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)

𝑍 𝑍 2
R1s = 2( )3/2 𝑒 −𝑍𝑟/𝑎0 R21s = 2( )3/2 𝑒 −𝑍𝑟/𝑎0
𝑎0 𝑎0

(b) The probability of finding electron at points

along a line drawn from the nucleus outward r
for H 1s orbital.

60
1s Orbital and Electron Density
How does the total electron density of a spherical
shell change with radius r?

= total area × probability at one point

= 4r2×R2(r)

That is, Radial probability distribution function

Cross section of H 1s orbital probability Radial probability distribution function

61
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-).
Most probable distance (rmp)

For H, the maximum is at r = 0.529 Å, the radius of H.

62
Exercises
1. Give the name of the listed functions

(a)  Wave function (atomic orbital)

(b) Y(q, f) Angular wave function

r

(c) R(r) Radial wave function

(d) R2(r) Probability distribution function

(e) 4r2R2(r) Radial Probability distribution function

(f) 2 Electron density

63
2.5.2. Shapes of s, p, d and f orbitals
Shapes of s, p and d orbitals
z

s Where do they come from?

y
x

Why they have different shape?

p

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?
64
The shape of s and p orbitals: let’s try to visualize
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  Probability of finding e- also depends on angles
1 1 3 sinqcosf px
2 
Try φ=0 and 90°
-1 1 3 sinqsinf py
2 

(rqf)
q r

f
x
65
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
+ and – represents positive and negative side of a simple sin wave
66
Different Ways of Presenting p Orbitals

y
x
+

pz

py +

67
Nodal property of p orbitals

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

Node: region having zero electron density 2 = 0
z z z

+ y y
y

x - x x

Since such nodes are related to directions (angles), they are termed as angular nodal
surface (plane), or simply angular node. (we will talk about radial nodes later)

p orbitals contain one angular nodal surfaces (planes)

68
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

69
Nodes of d Orbitals
d orbitals contain two angular nodal surfaces (planes).

70
Nodal surface of dz2 ??

71
Nodes of d Orbitals

72
Shapes of f Orbitals (reference only)

How many angular nodes does a f Orbital has?

73
Summary: Shapes of s, p and d Orbitals
z Number of nodes

s 0
y
x

1
p

pz px py

d
2
dxz dyz dxy dx2-y2 dz2
Total # of angular nodes =
Very important! You should remember them. l (angular momentum quantum number)
74
Exercise

1. Sketch the (angular) shapes of py and dyz orbitals. Indicate the

nodes for each orbitals.

py dyz
z

75
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?

76
ns Atomic Orbitals

• Generated from RnsxYs

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

• Rns are different

• Shapes of ns orbitals depend on n.

Examples of Rns (for reference)

At some r value, R2s = 0!!

R1s: 2( 𝑍 )3/2 𝑒 −𝑍𝑟/𝑎0 R2s:

𝑎0

77
The 1s, 2s, and 3s orbitals
Representations of the electron probability density:
overall 2D-cross section ¼ portion 4r2R(r)2
0 node 𝑍 3/2 −𝑍𝑟/𝑎
1s: 2( ) 𝑒 0
𝑎0
Radial Node 1 node

2s:

Radial Node 2 node

3s:

➢ Relative sizes: larger ns, large size

➢ Nodal characteristics: larger ns, more nodes

78
Comparisons of 1s, 2s and 3s orbitals

larger ns, more nodes

79
The 1s, 2s, and 3s orbitals
How would you present 1s, 2s and 3s orbitals with signs?
Electron density (2ns):

1s
2s 3s

Ys: +

Rns:

+
-
-
AO of ns: ns = Rns×Ys +
+

1s 2s 3s
80
np Atomic Orbitals

• Derived from p orbitals.

z z z

y y y

x x x

• As wave functions of np = Rnp×Yp, the overall shape of a np orbital will depend

on n.

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

81
 Some radial wave functions R(r) for hydrogenic atom

corresponding

Electron Density Distribution of 2p and 3p Orbitals

n l R(r) orbitals
3/2 R 1s
Z
1 0 2
a0 e-Zr/a0

1 3/2
2 0 Z Zr
a0 2- e-Zr/2a0 R 2s
2 2 a0

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

2 3/2
3 0 Z 18Zr 2Z2r2 -Zr/3a0 R 3s
27- e
81 3 a0 a0 +
a02
3/2

A 2p orbital: 3 1
6
4
a0wave afunctions
81 radial
Some 0 a02
e
Z
R(r)
6Zr
for hydrogenic atom
-
Z2r2
-Zr/3a0 R 3p

3 2n 4r2R2(r),
4 Z
3/2
Z2r2 R 3d corresponding
l
81 30 a0 e-Zr/3a
R(r) 0
a02 orbitals
3/2 R 1s
a0 = 0.529 A Z
1 0 2
a0 e-Zr/a0

1 3/2
2 0 Z Zr
a0 2- e-Zr/2a0 R 2s
2 2 a0

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

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

A 3p orbital: 3
2 3/2
0 Z
27-
18Zr
a0 +
2Z2r2 -Zr/3a0 R 3s
e
•
81 3 a0
But there is also a radial node. 3/2
a02
4 Z 6Zr Z2r2
3 1 - R 3p
81 6 a0 a0 e-Zr/3a0
a02
4 3/2
Z Z2r2 R 3d
3 2 e-Zr/3a0
4r2R2(r),30 81 a0
a02

+ - + - a0 = 0.529 A

The difference between angular node and radial node?

82 radial node
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. (for simplicity)

+
83
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 + - + -

84
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.

85
Electron Density Distribution of the d orbitals

86
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 = n-1

Number of radial nodes = n-l-1

Number of angular nodes = l

Very important!
87
Summary of Electron Density of Orbitals in the First Three Shells

Density plots (Ψ2)

3s 3p 3d

2s 2p

1s

88
From Bohr’s model to quantum mechanical model

electron in atomic orbitals without fixed

electron in orbits with fixed radii and
radii but with fixed energies oscillating
fixed energies around the nucleus (each
around the nucleus as a wave (each
“orbit ” is a 2D-disk-like-circle)
orbital is a 3D standing wave)

Each “shell ” (each n”) Each “shell ” (each “ n”)

corresponds to one “orbit” contains n2 orbitals
89
Summary of Quantum Model of H Atom
5th

• Orbitals are standing waves

with fixed energy
• Each “shell ” (each “ n”)
contains n2 orbitals
• 3 quantum numbers (n, l, ml)
defines the AO
• ms defines e spins

➢ Understanding of the atomic structure is the key to build your chemistry foundations!

90
Visualization of atomic orbitals

https://www.falstad.com/qmatom/

2s 2p

3s 3p 3d

1s
4s 4p 4d 4f
Can you count the # of nodes…
91
 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.

92
END