General Chemistry I

Introduction to radioactivity & quantum theory

Course instructor: Vincent Wing-hei Lau
Autumn semester
State-of-the-art from late 19th to early 20th century
Late 19th century Early 20th century
• Thermodynamics based on steam engine • Establishment of relativity & quantum theory
• Maxwell equation for electromagnetic radiation • Atomic theory based on quantum mechanics
• Gas laws and Dalton’s atomic theory • Wave theory, uncertainty principle and bonding
• Faraday’s law of electrochemistry • Discovery of radioactivity and nuclear reactions
“There is nothing new to be discovered in physics now. All
that remains is more and more precise measurement.” “I must confess it was very unexpected and I am very
Paraphrasing Philipp von Jolly’s startled at my metamorphosis into a chemist.”
advice to Max Planck Ernest Rutherford

1918 Nobel prize in

physics for “his discovery
of energy quanta." 1908 Nobel prize in chemistry for
“investigations into the disintegration
“All science is either physics or stamp collecting” of the elements, and the chemistry of
radioactive substances."
Ernest Rutherford
Electromagnetic radiation
Classical wave model
• Light – thought to be wave (Young, 1802) but later found to have properties of both
wave and particle (de Broglie, 1924)
• Describing a wave (water wave, violin string, light)
➢ Wavelength: distance of crest-to-crest or trough-to-trough; represented by Greek
letter lambda λ, unit metre†
➢ Frequency: number of cycles per second; represented by Roman letter f or Greek
letter nu ν, unit per second (s–1) or hertz (Hz)
➢ Amplitude: height of wave crest or depth of wave trough
➢ Speed: distance per time, equivalent to frequency × wavelength
Gif source: https://www.laguarimba.com/
➢ Unit analysis: wavelength × frequency = m s–1
s=ν×λ
➢ Phase: fraction of a cycle covered

† systeme internationale unit

 Superimposition
Electromagnetic radiation of two waves

Classical wave model

+ =
• Multiple waves superimpose on each other (interference)
• Constructive interference: two identical waves adding onto
each other to have 2× amplitude (waves are in phase) Figure source: Gale Rhodes, Crystallography made crystal clear 3 Ed.

• Destructive interference: two waves identical except their path

of travel is such that the crest of one meets the trough of the Constructive
other (waves are out of phase) interference
• Diffraction: wave spreading out around the edge of an object or a + =
narrow aperture (small hole), accompanied by interference
• Example: diffraction of water waves through two slits

Destructive
interference

+ =

Figure source: https://www.chemistryworld.com/news/quantum-double-slit-experiment-done-with-molecules-for-the-first-time/4014819.article

Electromagnetic radiation
Electromagnetic spectrum & wave properties of light
• Young’s double slit experiment in 1802 demonstrates
light has wave properties (diffraction)
• Maxwell’s equation of electromagnetisms
Figure 7.5 from textbook

• Einstein’s theory of relativity: constant speed of light at

2.998×108 m s–1 (represented by letter c)

Figure 7.3 from textbook

• If speed of light wave constant, and c = ν × λ
then λ–1 ∝ ν i.e. ν↑ λ↓ and ν↓ λ↑
• All light wave same speed, differing only in ν or λ
• Amplitude of light wave related to intensity/brightness;
wavelength/frequency related to “colour”
Electromagnetic radiation
Electromagnetic spectrum & wave properties of light
• Monochromatic light has single wavelength; opposite
is polychromatic light (many wavelengths)
Light
• Coherence: when the sources of waves have identical
source
frequency and phase
• Collimation: parallel ray with minimal spread

• Polarisation: orientation of the oscillation

• Convention for light: polarisation refers to direction
of electric field
• Polarised light has light waves all with E (and B)
pointing in the same direction

Polarized filters found on Alibaba.com

Electromagnetic radiation
Electromagnetic spectrum & wave properties of light
• Spectrum of electromagnetic radiation: continuum from
radio wave (λ >103 m) to gamma rays (λ <10–11 m)
• Non-SI units common depending on applications:
• X-ray: 1 Å = 10–10 m
• Infrared spectroscopy typically uses cm–1

Figure 7.3 from textbook

Electromagnetic radiation
Example problem 1
Convert the following electromagnetic Electromagnetic wave: c = λ × ν where c = 2.998×108 m s–1 keeping units
radiation from wavelength to frequency: the same:
a) λ = 1.00 Å (x-ray) 10−10 𝑚
a) Since 1 Å = 10–10 m ⇒ 1.00 Å × 1Å
= 10−10 𝑚
b) λ = 325 cm (radiowave) 𝑐 2.998×108 𝑚 𝑠 −1
𝜈= = = 2.998 × 1018 𝑠 −1 = 3.00 × 1018 𝐻𝑧 (3 sig. fig.)
c) λ = 473 nm (blue light) 𝜆 10−10 𝑚

10−2 𝑚
• Unit analysis to check correct unit b) Since 1 cm = 10–2 m ⇒ 325 𝑐𝑚 × 1 𝑐𝑚
= 3.25 𝑚
conversion and correct equation being 𝑐 2.998×108 𝑚 𝑠 −1
applied 𝜈= = = 9.22 × 107 𝑠 −1 (3 sig. fig.)
𝜆 3.25 𝑚

• Keep unit consistent to avoid mistakes

10−9 𝑚
c) Since 1 nm = 10–9 m ⇒ 473 𝑛𝑚 × 1 𝑛𝑚
= 473 × 10−9 𝑚
𝑐 2.998×108 𝑚 𝑠 −1
𝜈= = = 6.34 × 1014 𝑠 −1 (3 sig. fig.)
𝜆 473×10−9 𝑚
Electromagnetic radiation
Example problem 2
2. Some diamonds appear yellow because they contain impurities that absorb purple light of frequency 7.23×1014 Hz.
Calculate the wavelength in nm and Å of the absorbed light.

Electromagnetic wave: c = λ × ν where c = 2.998×108 m s–1: • Light wave not absorbed reaches our eyes
• Perceive as complementary colour as
𝑐 2.998×108 𝑚 𝑠 −1 given by colour wheel
𝜆= = = 4.15 × 10−7 𝑚
𝜈 7.23×1014 𝑠 −1 • Example: if purple light absorbed, yellow
light not absorbed and reaches our eyes
Answering to 3 sig. fig.
1 𝑛𝑚
Since 1 nm = 10–9 m ⇒ 4.15 × 10−7 𝑚 × 10−9 𝑚
= 415 𝑛𝑚

1Å
Since 1 Å = 10–10 m ⇒ 4.15 × 10−7 𝑚 × 10−10 𝑚
= 4.15 × 103 Å

Figure 23.15 from textbook

Electromagnetic radiation
Particle properties of light
• As light diffracts, light understood to be electromagnetic wave in 19th century
• Wave model of light cannot explain blackbody radiation and photoelectric effect

Blackbody radiation
• Light emitted when objected is “hot”
• Spectrum of emitted light depends on temperature
• Hotter the object, more light emitted at lower wavelength
• Coal 1000–2000 K ⇒ mostly red and infrared
• Sun 5000–6000 K ⇒ mostly visible
• Ideal black body: object that absorbs all incident radiation
• Classical physics cannot model the observed spectrum
Electromagnetic radiation
Particle properties of light
• As light diffracts, light understood to be electromagnetic wave in 19th century
• Wave model of light cannot explain blackbody radiation and photoelectric effect

Photoelectric effect
• In an unconnected circuit with electric field, irradiation above a certain
frequency of metal produces an electric current
• Since current is flow of electrons, so light transferring energy to propel
electrons from metal surface
• Different minimum frequency for different metals
• Immediate current flow with no lag time, but current proportional to
brightness of light
• Classical mechanic cannot explain the minimum frequency, or why electrons do
not need to be “charged” with (light) energy before emission

Figure 7.7 from textbook

Quantisation of energy and quantum theory
Particle properties of light
• Both black body radiation and photoelectric effect explainable if light is
considered to have properties of particles

• Each light particle – photon – has energy E = hν

i.e. energy is proportional to frequency with constant of proportionality to
be h, Planck’s constant ( 6.626 × 10–34 J·s )
• Light at a given wavelength/frequency cannot take on any value;
• Energy of light is quantised and comes in discrete amount rather than
a continuum
• The smallest is the energy in one photon (hν), the next smallest
comes with two photons (hν) etc
• Energy related to frequency/wavelength rather than amplitude as in
classical physics
• Intensity (brightness) of light related to number of photons Representation
of a light pulse
➢ Possible to have high energy light of low intensity
Figure 7.7 from textbook
Quantisation of energy and quantum theory
Particle properties of light – explaining photoelectric effect
Since energy related to frequency/wavelength as given by E = hν
• Threshold frequency related to minimum energy of light
required to knock electron out of a material
• Energy to take electron out of a material called work function
(represented by capital Greek letter phi Φ)
• Unit of work function same as energy: J or electron volt (1 eV
= 1.602×10–19 J) Metal Φ / eV
• Different materials hold electrons with different strength Au 5.4
(different values for work function); basis of x-ray Cu 5.0
photoelectron spectroscopy
Fe 4.8
• No time lag because electrons do not “save up” energy from
Ni 5.2
light – either there is enough energy or not enough
Sn 4.4
• Current proportional to brightness: dim light means fewer
photons knocking electrons out of metal

Figure 7.7 from textbook

Quantisation of energy and quantum theory
Example problem 1 Example problem 2
What is the energy of one photon with a Calculate the energy of one photon with a wavelength of
wavelength of 1.20 cm (microwave)? 1×10–8 m (UV), 5×10–7 m (vis) and 1×10–4 m (infrared, IR)?

ℎ𝑐 ℎ𝑐 6.626×10−34 𝐽∙𝑠 ×2.998×108 𝑚 𝑠 −1

Planck’s equation: 𝐸 = ℎ𝜈 = 𝜆 𝐸 = =
𝜆 𝜆 𝑖𝑛 𝑚
Planck’s constant: 6.626 × 10–34 J·s
➢ 1 J = kg m2 s–2, so need to convert 1.20 cm to UV light : 2×10–17 J (1 sig. fig.)
metre: 1.20 cm = 1.20 × 10–2 m
vis light : 4×10–19 J
➢ Speed of light in m s–1: 2.998 × 108 m s–1
IR light : 2×10–21 J

ℎ𝑐 6.626×10−34 𝐽∙𝑠 ×2.998×108 𝑚 𝑠 −1

𝐸 = = Longer wavelength ⇔ Lower frequency ⇔ lower energy
𝜆 1.20×10−2 𝑚
= 1.66 × 10–23 J (3 sig. fig.)
From energy quantisation to atomic structure
By late 19th and early 20th century: Evolution of atomic model
• Gas laws and thermodynamics • Dalton’s model of indivisible constituents of atoms
• Chemical reactions and conservation of mass • Thompson’s discovery of electrons and proposed “plum pudding”
• Early spectroscopy of stars and chemicals model (1904): light negatively charged particles on heavier
positively charged particles
• Radioactivity

• Rutherford’s gold foil experiment (1908-1915): nucleus much

smaller than the size of atom; proposed an atomic model similar
to solar system of negative electrons surrounding positive protons
• Cannot explain stability of electrons in orbit
• Cannot explain spectra

Figure source: American Institute of Physics

https://history.aip.org/exhibits/cosmology/tools/tools-spectroscopy.htm
Atomic spectroscopy & atomic structure
• Absorption lines in sunlight (and light from other stars) observed Figure source: American Institute of
Physics
when prism used with telescope (Fraunhofer, prior 1850) https://history.aip.org/exhibits/cosmol
ogy/tools/tools-spectroscopy.htm

• Flame test and flame spectroscopy developed by Bunsen and

Kirchhoff for identifying elements (around 1860)
• Spectrum for hydrogen (lightest element) by Rydberg leading to
the so-called Rydberg equation:
1 1 1
=𝑅 −
𝜆 𝑛12 𝑛22

where R is Rydberg constant (1.097×107 m–1) and n1 and n2 are Figure source:
positive integer with n2 > n1 https://www.sciencehistory.org/histori
cal-profile/robert-bunsen-and-gustav-
kirchhoff
➢ For visible series, n1 = 2 and n2 ≥3

Figure 7.8 and 7.9 from textbook

Atomic spectroscopy & atomic structure
• Elements have characteristic wavelengths • Spectroscopy still used today to determine the elemental
composition of substances and stars

Sr Cu

Figure source: American Institute of Physics

https://history.aip.org/exhibits/cosmology/tools/
tools-spectroscopy.htm

• Amount of light absorbed is proportional to amount of

that element ⇒ allows quantification (Beer-Lambert law)

https://www.facebook.com/IFLScience/photos/a.45
6449604376056/1150884458265897/?type=3&_rdr
Textbook figure B7.1, B7.3 & 7.4
From energy quantisation to atomic structure
• Problems with Rutherford’s atomic model: • Bohr model (1913) incorporates Planck’s and Einstein’s ideas
o Cannot explain stability of electrons in orbit about quantisation to explain atomic spectra:

o Cannot explain spectra ➢ Electrons can take “orbits” with specific radius, labelled
1 1 1 with a quantum number n, but cannot take any other
=𝑅 − 𝑛2 orbits of other radii
𝜆 𝑛12 2

➢ Larger n ⇒ larger radius ⇒ more energetic

➢ Energy transferred (absorbed or emitted) only when
electrons change orbits (violates classic physics as orbiting
electrons should always emit energy)
➢ Light observed in spectrum (absorbed or emitted)
depends on differences in “orbit” energy
𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = Δ𝐸𝑎𝑡𝑜𝑚 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = ℎ𝜈
• Successful in explaining spectral lines in hydrogen (but fails to
explain multi-electron elements, nor why certain orbits exist)

Textbook figure 7.11

From energy quantisation to atomic structure
Bohr’s atomic model
• Orbit with lowest energy (n = 1) called ground state
• Orbit with higher energy (n = 2, 3, 4 …) called excited state
• Energy exchanged related to how an electron changes orbit

Energy exchange:
• Electrons absorb energy and jump to a higher energy orbit
(dark lines in spectra of stars)
• Electrons can fall to lower energy orbit, accompanied by
energy emission (lines in elemental spectra)
• Absorbed/emitted energy corresponds to difference in
orbital energy, and energy takes form of light energy of the
corresponding wavelength:
𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = Δ𝐸𝑎𝑡𝑜𝑚 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = ℎ𝜈

Textbook figure 7.10 & 11

 From energy quantisation to atomic structure
Energy exchange in Bohr’s atomic model
• Electrons absorb energy and jump to a higher energy orbit
• Dark lines in spectra of stars
• Light absorbed by electrons is light not reaching your eyes/telescope
• Electrons can fall to lower energy orbit, accompanied by energy
emission (lines in elemental spectra)
Figure source: American Institute of Physics
• Line spectra from flame spectroscopy https://history.aip.org/exhibits/cosmology/tools/
tools-spectroscopy.htm

• Light emitted by relaxing electrons is light reaching your eyes

perceived as colour

Textbook figure 7.9 & 10

From energy quantisation to atomic structure
Energy levels in Bohr’s atomic model for hydrogen
• Energy exchange when electrons jump up from or fall
down to energy levels analogous to a falling object
(gravity, picture a waterfall)
o Gravity: energy conversion depends on height
o Height is relative – needs reference point
• Combining Rydberg & Planck equation:
1 ∆𝐸 1 1
= =𝑅 2 − 𝑛2
𝜆 ℎ𝑐 𝑛𝑓𝑖𝑛𝑎𝑙 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

• Recall large n ⇒ large radius ⇒ large energy

Set reference point to n = ∞ so one fraction = 0
Convention: lower position has lower potential
energy (negative sign) 1st excited state (n=2) E = –5.45×10–19 J
1
𝐸 = −2.18 × 10−18 𝐽
𝑛2 Ground state (n=1) energy: –2.18×10–18 J

Textbook figure 7.11

From energy quantisation to atomic structure
Energy levels in Bohr’s atomic model for hydrogen
1 1
• Equation ∆𝐸 = −2.18 × 10−18 𝐽 2 − 𝑛2
𝑛𝑓𝑖𝑛𝑎𝑙 𝑖𝑛𝑖𝑡𝑖𝑎𝑙
calculates energy exchanged (absorbed or emitted) for
any given transition in H atom
▪ If energy absorbed, nfinal > ninitial, so E > 0 ⇒ input of
energy to excite electron to a higher place
▪ If energy emitted, nfinal < ninitial, so E < 0 ⇒ getting
energy out of atom in the form of light
▪ Energy of light given by Planck’s equation E = hν
• Ionisation energy – energy input required to take out an electron
➢ Same as making an electron jump from n=0 to n=∞
➢ Eionisation = 2.18×10–18 J positive because energy input required
➢ Eionisation often quoted in J mol–1 i.e. energy input required to ionise 1 mol H

𝐸𝑖𝑜𝑛𝑖𝑠𝑎𝑡𝑖𝑜𝑛 = 2.18 × 10−18 𝐽 𝑎𝑡𝑜𝑚−1 × 6.022 × 1023 𝑎𝑡𝑜𝑚 𝑚𝑜𝑙 −1 = 1.31 × 106 𝐽 𝑚𝑜𝑙 −1 Textbook figure 7.11
From energy quantisation to atomic structure
Example problem 1
A hydrogen atom in the ground state (n=1) absorbs a photon of UV light and its electron enters n=4. Calculate the
change in energy of the hydrogen and the wavelength of the incident photon.

1 1
Using modified Rydberg equation ∆𝐸 = −2.18 × 10−18 𝐽 2
𝑛𝑓𝑖𝑛𝑎𝑙
− 2
𝑛𝑖𝑛𝑖𝑡𝑖𝑎𝑙
1 1 15
= −2.18 × 10−18 𝐽 − = −2.18 × 10−18 𝐽 × − = 2.04 × 10−18 𝐽
42 12 16

Energy positive denoting energy input

ℎ𝑐
From energy ΔE, use Planck equation to find wavelength of light: ∆𝐸 = 𝜆
ℎ𝑐 6.626×10−34 𝐽 𝑠 × 2.998×108 𝑚 𝑠 −1
⇒𝜆 = = = 9.74 × 10−8 𝑚 = 97.4 𝑛𝑚
∆𝐸 2.04×10−18 𝐽
From energy quantisation to atomic structure
Example problem 2
An electron in the hydrogen atom in the excited state n=6 drops to n=3. Calculate the change in energy of the atom
and the wavelength of the light emitted in Å.

1 1
Using modified Rydberg equation ∆𝐸 = −2.18 × 10−18 𝐽 2
𝑛𝑓𝑖𝑛𝑎𝑙
− 2
𝑛𝑖𝑛𝑖𝑡𝑖𝑎𝑙
1 1 3
= −2.18 × 10−18 𝐽 − = −2.18 × 10−18 𝐽 × = −1.82 × 10−19 𝐽
32 62 36

Energy negative denoting energy given off from atom

ℎ𝑐
From energy ΔE, use Planck equation to find wavelength of light: ∆𝐸 = 𝜆
ℎ𝑐 6.626×10−34 𝐽 𝑠 × 2.998×108 𝑚 𝑠 −1
⇒𝜆 = = = 1.09 × 10−6 𝑚 Note: wavelength must be positive
∆𝐸 1.82×10−19 𝐽
1Å
Since 1 Å = 10–10 m, 𝜆 = 1.09 × 10−6 𝑚 × = 1.09 × 104 Å
10−10 𝑚
From energy quantisation to atomic structure
Wave-particle duality
• Bohr’s model rationalises energy exchange/transition, but
not electron stability in “orbit”
• From Einstein’s E = mc2 equating matter with energy, and
from the particle nature of light, de Broglie proposed
matters also have wave-like properties
ℎ𝑐
Representation of a
𝐸= 𝑚𝑐 2 = light/particle pulse De Broglie,
𝜆 Nobel prize for
For particles travelling at speed v (not speed of light): physics 1929

ℎ
𝜆= Object Mass (g) Speed (m s–1) λ (m)
𝑚𝑣
• Equation gives de Broglie wavelength, the wavelength of a Fast electron 9×10–28 6×106 1×10–10
particle assuming it has wave properties 1 g mass 1.0 0.01 7×10–29
• Implication: everything has properties of both matter and Car at 60 km/h 1×106 17 4×10–41
wave (wave-particle duality) BUT not always observable
Earth 6×1027 3×104 4×10–63
(e.g. wavelength below detection limit for everyday
objects)
From energy quantisation to atomic structure
Wave-particle duality
• Electrons orbiting nucleus have wavelength as given by
ℎ
𝜆 = 𝑚𝑣 to have similar order of magnitude to atomic
size (10–10 m)
• Electron orbit treated as a standing wave (analogous
to a rope tied on two ends)
➢ Electrons stable in orbit if orbit is equivalent to
𝑛
multiples of wavelength i.e. 2 𝜆
➢ Stable orbits are ½ λ for n=1 (ground state), λ for
n=2 (first excited state) etc
➢ Non-multiple of wavelengths not allowed
➢ Explains electron stability in orbit and discrete
energy levels in Bohr’s model

Textbook figure 7.12

From energy quantisation to atomic structure
Example problem 1 on de Broglie wavelength
Find the de Broglie wavelength of an electron with a speed of 1.00×106 m s–1, given that mass of electron is
9.11×10–31 kg.

From de Broglie equation and looking up data sheet for Planck’s constant:
ℎ 6.626×10−34 𝐽 𝑠
𝜆= 𝑚𝑣
= 9.11×10−31 𝑘𝑔 ×1.00×106 𝑚 𝑠 −1
= 7.27 × 10−10 𝑚

For unit analysis, either keep SI unit or use 1 J = 1 kg m2 s–2

Problem 2: What is the speed of an electron with a de Broglie wavelength of 100 nm?

ℎ 6.626×10−34 𝐽 𝑠
From above: 𝜆 = = = 1.00 × 10−7 𝑚 ⇒ 𝑣 = 7.27 × 103 𝑚 𝑠 −1
𝑚𝑣 9.11×10−31 𝑘𝑔 × 𝑣
Applications based on particle-wave duality
• Wave properties of light allowing us to see:
diffraction, refraction and interference
❑ Wavelength for UV-visible light >350 nm ⇒
cannot image anything smaller 100 nm
(theoretical limit)
❑ X-ray imaging possible only recently as no
suitable “lens” for focusing x-ray available
before
• Electrons have de Broglie wavelength around Å
scale (see previous example)
➢ Also has wave properties allowing us to see
➢ Imaging with atomic resolution possible – From NCKU Instrument Development Centre
Electron microscopy image of
particles inside Li ion batteries
basis of electron microscopy
• Imaging with neutron (λ ≈ 1 nm) also possible –
basis of neutron microscopy demonstrated 20
years ago
https://phys.org/news/2004-07-neutron-microscope.html
Particle-wave duality
• All matters have properties of particle and wave, the
two related by de Broglie’s equation
ℎ =𝑝×𝜆
where p is momentum (p = m × v)
• Light also has momentum, as demonstrated by the
Compton experiment:
Compton, Phys. Rev. 1923, 21, 483
• Light (x-ray) losing momentum after being
scattered by a solid
• Momentum loss observed as λ increase

• Basis of Compton scattering experiment – analytical

technique to understand “electronic structure” of
materials
Particle-wave duality Fast shutter speed photography Motion blurred

• Since particles have wave-like properties, limit to how

exact one can determine position and speed of particle
• “Exactness” or “uncertainty” of the measurement given
by Heisenberg’s uncertainty principle:
ℎ https://www.malibumakos.com/ocean-waves/ https://www.amazon.com/Posterazzi-DPI12305497-
blurred-motion-America/dp/B07H9JXJXT
Δ𝑥 ∙ 𝑚Δ𝑣 ≥
4𝜋
Δ refers to measurement uncertainty of a quantity; note • Uncertainty principle also in
ℎ ℏ terms of time and energy:
that some texts use ℏ = 2𝜋, so Δ𝑥 ∙ 𝑚Δ𝑣 ≥ 2
ℎ
• In word, the more exact the position of a particle is Δ𝐸 ∙ Δ𝑡 ≥
determined, the bigger the error is in measuring its 4𝜋
velocity, and vice versa • Example: the more exact one
measures the time an
electron spends in an excited
state, the more error is in
measuring its energy
Representation of a light/particle pulse • Explains why spectral lines
has a “width”
Particle-wave duality
Example problem 1
An electron moving near an atomic nucleus has a speed of 6×106 m s–1 ±1%. What is the uncertainty in its position?

Speed uncertainty, Δv, is 1% of 6×106 m s–1, which is 6×104 m s–1

ℎ
Applying Heisenberg’s uncertainty principle Δ𝑥 ∙ 𝑚Δ𝑣 ≥ and using mass of electron (slide 28):
4𝜋
ℎ 6.626×10−34 𝐽∙𝑠
Δ𝑥 ≥ = = 9.65 × 10−10 𝑚 ⇒ Δx ≥ 1×10–9 m (1 sig. fig.)
4𝜋∙𝑚Δ𝑣 4𝜋 × 9.11×10−31 𝑘𝑔 × 6×104 𝑚 𝑠 −1

Positional uncertainty bigger than size of atom ⇒ No idea where electron is around nucleus
Particle-wave duality
Example problem 2
How accurate can one know the position of a ball of mass 0.142 kg moving at a speed of 45.0 m s –1 ±1.00%?

Speed uncertainty, Δv, is 1% of 45 m s–1, which is 0.45 m s–1

ℎ
Applying Heisenberg’s uncertainty principle Δ𝑥 ∙ 𝑚Δ𝑣 ≥ and using mass of electron (slide 28):
4𝜋
ℎ 6.626×10−34 𝐽∙𝑠
Δ𝑥 ≥ = = 8.25 × 10−34 𝑚 ⇒ Δx ≥ 8.25×10–34 m
4𝜋∙𝑚Δ𝑣 4𝜋 × 0.142 𝑘𝑔 ×0.45 𝑚 𝑠 −1

For everyday object of macro scale, uncertainty and other phenomenon related to quantum effect not discernible.
Quantum mechanical model of atom
• Bohr’s model of H atom treating electron orbiting nucleus as
standing wave with de Broglie wavelength suggests the
electron’s position and orbiting speed known
⇒ violates uncertainty principle
• Instead, the electron needed to be treated as wave
mathematically described as a wave function (represented
by Greek letter psi ψ)
• ψ is 3D; just as a standing wave (1D) can have multiple Textbook figure 7.11 & 12
solutions with one parameter n, ψ has three parameters
n, l, m (explained later)
• ψ has no physical meaning, but mathematical treatment
tells you the most likely location of an electron around
nucleus (3D)
• To find ψ, the Schrödinger equation is solved:
ℋ𝜓 = 𝐸𝜓
where Ĥ is the Hamiltonian operator and E is energy Some “3D plots” of ψ with different
values for n, l, m
Quantum mechanical model of atom
Mathematical aspects of Schrödinger equation 𝓗𝝍 = 𝑬𝝍
• Operator Ĥ (circumflex ^ indicates operator) is the mathematical treatment to find energy of something
➢ Just as a function f(x) operates on variable x, operator Ĥ operates on function ψ
➢ Hamiltonian operator Ĥ finds the total energy of a system, summing kinetic and potential energy:
1 𝑝2
▪ For kinetic energy, a bit like 𝐸𝑘𝑖𝑛𝑒𝑡𝑖𝑐 = 𝑚𝑣 2 = but 3D and written as operator
2 2𝑚
▪ Potential energy from interaction between proton and electron
• Ĥ operating on wavefunction ψ gives back the same ψ, but multiplied by constant E
➢ We say ψ is an eigenfunction (eigen means same), and E is eigenvalue
• Solving Schrödinger equation means finding ψ, so that after operation returns ψ
➢ Many solutions depending on the three parameters
• ψ has no physical meaning, but has statistical-probabilistic information about the electron (Copenhagen interpretation)
➢ |ψ2| gives probability density ⇒ where you are most likely to find the electron
Quantum mechanical model of atom
Probability density related to wavefunction ψ
• Probability density tells you likelihood of something
➢ Example – throwing two dice: most likely sum is 7 (1+6, 2+5 etc), least
likely sums are 2 and 12 (1+1, 6+6)
➢ Plot of probability density function gives graphical representation
• For each ψ that is solution to Schrödinger equation, |ψ2| gives probability
density around nucleus
➢ Example – lowest energy state: probability density radial from nucleus
▪ Most probable finding e– around nucleus
▪ Least probable the further away but non-zero
➢ Total probability at a given distance from nucleus plotted to
show where electron most likely found
▪ Since probability non-zero even with large r, atoms visualised as
volume where electron has 90% probability (i.e. volume where
electron is there 90% of the time)
Quantum mechanical model of atom
Probability density related to wavefunction ψ
• Each solution of Schrödinger equation, ψ, is an atomic
orbital with a specific energy 90%

• Similar to Bohr’s model, where each orbit has a specific

energy, but…
• Orbital ψ not an orbit; better described as
mathematical construct
• Putting an electron in an orbital ψ means that the electrons
likely to be found in region as plotted for ψ
• Atom visualised as volume where electron has 90%
probability of being found there (i.e. volume where electron
is there 90% of the time)
• Drawing known as electron cloud ⇒ region where Some “3D plots” of ψ
electrons likely to be found

What are the solutions to Schrödinger equation, ψ?

Quantum mechanical model of atom Textbook figure 7.12

Solutions to Schrödinger equation, ψ

• Standing wave (one-dimensional) has infinitely many solutions depending on
parameter n; energy increases with n
• Wavefunction ψ (3D) has three parameters, the quantum numbers n, l, m,
each with a special name

Principal quantum number, n Angular momentum quantum number l Magnetic quantum number ml
• Positive integer (1, 2, 3… etc) • Integer from 0 to n-1 • Integer from –l through 0 to +l
• Shows orbital size and relative • Shows shape of orbital • Shows orientation of orbital around
distance from nucleus nucleus
• Specifies energy level (high n • Number of ml value equals 2l+1
means higher energy)

Some “3D plots” of ψ, depending on the three

parameters of n, l and m
Quantum mechanical model of atom
Three quantum numbers of ψ

Name, symbol & properties Allowed values Quantum numbers

Principal number, n 1, 2, 3 … 1 2 3
(size, energy)

Angular momentum, l 0 to n–1 0 0 1 0 1 2

(shape)

Magnetic, m (or ml) –l, –l+1, …, 0, 0 0 -1 0 1 0 -1 0 1 -2 -1 0 1 2

(orientation) …, l–1, l
Quantum mechanical model of atom
Quantum numbers, energy levels and atomic orbitals
• Principal number n indicates an atom’s energy level
• Smaller n, lower energy, closer to nucleus
• Naming in physics based on spectroscopy: K for n=1, L
for n=2, M for n=3, N for n=4
• Angular momentum l indicates subshells (also called
sublevels); each subshell has a label:
• l=0 s subshell
• l=1 p subshell
• l=2 d subshell
• l=3 f subshell
• Lettering spdf derived from spectroscopic description
(sharp, principal, diffuse, fundamental)
• Magnetic m indicates how subshells s, p, d and f
orientate in space
Textbook figure 7.17
Quantum mechanical model of atom
s orbitals
• s orbital when l = 0: spherical centred at nucleus
• For n=1, we say “1s orbital”
• Hydrogen atom ground state
• Electron highest probability found near nucleus
• For n=2, we say “2s orbital”
• Most probable location of electron further out
from nucleus than 1s orbital
• Point of zero probability called node, similar to
point of zero magnitude in standing wave:

• For n=3 and so forth, “3s orbital” with n–1 nodes

Textbook figure 7.12 & 7.17

Quantum mechanical model of atom
p orbitals
• p orbital when l = 1 (must have n ≥ 2)
• Two symmetric regions (lobes) of high probability on either
side of nucleus
• Three possible orientations (3 values for m) ⊥ to each other
(contrast with the spherical s orbitals)
➢ For convenience, line each of the three along three
Cartesian axes, labelled as px, py and pz
• Node for each orbital is on ⊥ axis (i.e. px has node on yz plane,
py has node on xz plane etc)
➢ Node indicates zero probability of finding electron there
➢ Electron spend half the time in one node, the other half in
the opposite node Orbitals for n = 2, l = 1,
• Lowest energy p orbitals are when n=2 (2p orbitals); 3p m = -1, 0 and +1 ⇒ pointing along
orbitals larger than 2p, 4p larger than 3p etc three Cartesian axes

Textbook figure 7.18

Quantum mechanical model of atom
d orbitals
• d orbital when l = 2 (must have n ≥ 3)
• Five orientations corresponding to five values for m
(–2, –1, 0, 1, 2)
• Four of the five orientations have 4 lobes with two ⊥
nodal planes
• Three orientations off-axes on xy-plane, xz-plane and
yz-plane, labelled as dxy, dxz and dyz
• One orientated along two axes; for convenience,
orientated to lie on xy-plane and labelled as 𝑑𝑥 2−𝑦2
• Last d-orbital has two lobes along z-axis and donut on xy-
plane, divided by conical node; label as 𝑑𝑧 2
• Lowest energy d-orbitals are those with n=3 (3d orbitals);
analogous to before, 4d orbitals bigger than 3d, 5d bigger
than 4d etc
Orbitals for n = 2, l = 1, m = –2 to +2

Textbook figure 7.18

Quantum mechanical model of atom
f orbitals
• f orbital when l = 3 (must have n ≥ 4), with 7 orientations corresponding to 7 values for m (–3 to +3)
• More complex, multiple lobes and multiple nodal planes
• Less relevant than s-/p-/d-orbitals; unlikely to be encountered except for very specialised chemistry

Textbook figure 7.18

Quantum mechanical model of atom
Energetic comparison
• All ψ shown calculated for hydrogen atom having only one
electron and one proton
➢ Energy of orbitals depends only on principal quantum
number n
➢ s-, p-, d-orbitals have identical energy for same value of n
(chemistry term for same energy is “degenerate”) as
shown in figure
• All other elements have more than one proton/electron
➢ Need to account for additional nucleus-electron attraction
and electron-electron repulsion ⇒ Hamiltonian different,
different ψ solution to Schrödinger equation
➢ Energy different for different principal quantum number n

Textbook figure 7.21

Quantum mechanical model of atom
Sample problems 1
What values of angular moment (l) and magnetic (m) quantum numbers are allowed for a principal quantum number
(n) of three?

Value for l can be from 0 to n–1 ⇒ for n = 3, l can be 0 (s-orbital), 1 (p-orbital) and 2 (d-orbital)
Value for m can be from –l to 0 to +l ⇒ for l = 0, m = 0
⇒ for l = 1, m = –1, 0, 1 (px, py, pz orbitals)
⇒ for l = 2, m = –2, –1, 0, 1, 2 (dxy, dxy, dyz , 𝑑𝑥 2−𝑦2 , 𝑑𝑧 2 orbitals)

All orbitals possible, written as (n, l, m) are: (1, 0, 0)

(2, 0, 0) (2, 1, –1), (2, 1, 0), (2, 1, +1)
(3, 0, 0) (3, 1, –1), (3, 1, 0), (3, 1, +1)
(3, 2, –2), (3, 2, –1), (3, 2, 0), (3, 2, 1), (3, 2, 2)
Quantum mechanical model of atom
Sample problems 2
Give the name, magnetic quantum numbers, and number of orbitals possible for the given n and l quantum numbers:
a) n=3, l=2 b) n=2, l=0 c) n=5, l=1 d) n=4, l=3

Recall m can be –l to 0 to +l
a) m = –2, –1, 0, 1, 2 Principal number is 3, designation for l=2 is d, five values of m ⇒ five 3d-orbitals
b) m = 0 Principal number is 2, designation for l=0 is s, one value of m ⇒ one 2s-orbitals
c) m = –1, 0, 1 Principal number is 5, designation for l=1 is p, three values of m ⇒ three 5p-orbitals
d) m = –3, –2, –1, 0, 1, 2, 3 Principal number is 4, designation for l=3 is f, 7 values of m ⇒ seven 4f-orbitals
Quantum mechanical model of atom
Sample problems 3
What are the n, l and possible m values for the a) 2p, and b) 5f subshells?

a) 2p ⇒ principal number 2 p-orbital has l=1, so m can take –1, 0, +1

b) 5f ⇒ principal number 5 p-orbital has l=3, so m can take –3, –2, –1, 0, +1, +2, +3

Sample problem 4
Supply the missing quantum numbers or subshell names:
n l m Orbital name
a) ? ? 0 4p
b) 2 1 0 ?
c) 3 2 –2 ?
d) ? ? ? 2s
Lecture outcome
Light as electromagnetic waves Model of hydrogen atom
➢ Describing waves: wavelength & frequency ➢ Basics of spectroscopy based on electron transition
(“colour”), amplitude between energy levels (Bohr’s model)
➢ Wave behaviours refraction, superimposition, −18
1 1
Δ𝐸 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = −2.18 × 10 𝐽( 2 − 2 )
interference & diffraction 𝑛𝑓𝑖𝑛𝑎𝑙 𝑛𝑖𝑛𝑖𝑡𝑖𝑎𝑙
Quantum theory to account for failures of ➢ Particle-wave duality explaining electron’s stability in orbit
classical models (de Broglie wavelength λ = h·p–1)
➢ Spectrum of blackbody radiation, ➢ Heisenberg’s uncertainty principle limiting measurement
photoelectric effect, and spectral lines ℎ
accuracy in quantum systems Δ𝑥 ∙ 𝑚Δ𝑣 ≥ 4𝜋
1 1 1
➢ Rydberg equation 𝜆 = 𝑅(𝑛2 − 𝑛2 ) for n2 > n1)
1 2 Schrödinger equation describing wave-like electron
➢ Light as with properties of particles with ➢ Wavefunction as solution Schrödinger equation to indicate
energy given by E = hν probability of electron location and its energy
➢ Three quantum numbers (n, l, m) to plot the Ψ to
Schrödinger equation as orbitals around nucleus
Problem set
• State the relationship between wavelength, frequency and energy for electromagnetic radiation
• For the three waves below (not drawn to scale), answer the following:

Rank them in increasing frequency, increasing energy, increasing amplitude.

If wave B just barely fails to cause a current when shining on a metal, is wave A or C more likely to do so?
If wave B represents visible light, is A or C more likely to be IR
• Rank the following in increasing energy: x-ray, microwave, infrared, ultraviolet, visible light
• Rank these photons in terms of increasing energy: a) infrared (ν = 6.5×1013 s–1); b) microwave (ν = 9.8×1011 s–1); c)
ultraviolet (ν = 8.0×1015 s–1)
• A radio wave has a frequency of 3.6×1010 Hz. What is the energy in J of one photon of this radiation
• Which of the following electron transitions correspond to energy absorption and which to emission:
a) n=2 to n=4 b) n=3 to n=1 c) n=5 to n=2 d) n=3 to n=4
Problem set
• Use the Rydberg equation to find the wavelength in nm of the photon emitted when an H atom undergoes a
transition from n=5 to n=2. Calculate the energy difference for 1 mol of H atoms
• Use the Rydberg equation to find the wavelength in Å of the photon absorbed when an H atom undergoes a
transition from n=1 to n=3. Calculate the energy difference for 1 mol of H atoms
• An electron in a ground-state H atom absorbs a photon of wavelength 97.20 nm. To what energy level does it
transition to?
• How fast must a tennis ball of mass 56.5 g travel to have a de Broglie wavelength equal to that of green light (540
nm)?
• A sodium flame has a characteristic yellow colour due to emission of wavelength 589 nm. Using the equation for
de Broglie wavelength, what is the mass equivalence of one photon of this wavelength?
• Why could the Bohr model not predict spectra for atoms other than hydrogen?
• Under the so-called Copenhagen interpretation, is the physical meaning attributed to Ψ2?
• Explain why the energy of an orbital depends only on the principal quantum number n for only hydrogen but not
for other elements (e.g. why do 2s and 2p orbitals have the same energy for H but not other elements?)
Problem set
• Match the angular moment quantum number to the lettering designation (s, p, d, f) and to the shapes of the orbitals:
l = 0, 1, 2, 3 Lettering s, p, d, f Shapes:

Use the Rydberg equation to find the wavelength in Å of the photon absorbed when an H atom undergoes a
transition from n=1 to n=3. Calculate the energy difference for 1 mol of H atoms
• An electron in a ground-state H atom absorbs a photon of λ = 97.20 nm. To what energy level does it transition to?
• How fast must a tennis ball (56.5 g) travel to have a de Broglie wavelength equal to that of green light (540 nm)?
• A sodium flame has a characteristic yellow colour due to emission of wavelength 589 nm. Using the equation for de
Broglie wavelength, what is the mass equivalence of one photon of this wavelength?
• Why could the Bohr model not predict spectra for atoms other than hydrogen?
• What is the physical meaning attributed to Ψ2?
• For each of the following, give the sublevel designation, the allowable m values, and the number of orbitals:
a) n=4, l= 0 b) n=5, l=1 c) n=6, l=3
• For each of the sublevels, give the n and l quantum numbers, and number of orbitals: a) 5s b) 3p c) 4f