Chapter 7:
energy in the form of a wave
Quantum Theory of the Atom
Electromagnetic Spectrum
◆ electromagnetic radiation is classified by its λ
◆ Together, all types of electromagnetic radiation make
up the electromagnetic spectrum.
Electromagnetic Radiation or Radiant Energy:
characteristics of a wave:
◆ wavelength, λ – length from peak to peak or trough to
trough
◆ frequency, ν – number of peaks
that pass a set point per unit time
◆ for a wave: λν = c
c, speed of light = 3.00 x 108 m/s
Polychromatic vs. Monochromatic Light
Light that we see is white light –
◆ all the λ’s in the visible region present
i.e. polychromatic
◆ continuous spectrum
◆ when passed through a prism, white light is
scattered or separated into component colors
 Polychromatic vs. Monochromatic Light: Some Emission Spectra:
Atomic Line or Emission Spectra
Spectral Fingerprints of Elements
◆ monochromatic light – light of a single λ

◆ When atoms are raised in energy (i.e. excited) by

heating or other means, light is emitted.
light emitted is not white light;
not a continuous spectrum
◆ λ’s emitted are specific and characteristic;
these patterns and λ’s can be used to identify
elements
called line or emission spectra

Balmer, Rydberg & the Line Spectrum of Hydrogen Balmer, Rydberg & the Line Spectrum of Hydrogen

Balmer-Rydberg equation can be used for all lines

1885 – Johann Balmer studied line spectrum of H in the line spectrum of H:
and determined a relationship existing between
the lines in the visible region of the spectrum: 1 = R ( –––
1 – –––
1 )
–––
λ m2 n2
1 = R ( –––
––– 1 – –––
1 )
λ 2 2 n2 R, constant = 1.097 x 107 m–1
n and m are integers; n > m
n is an integer > 2 when m = 1, lines in UV region
R, constant = 1.097 x 107 m–1 when m = 2, lines in visible region
when m = 3, lines in IR region
 Max Planck (1900) & Quantized Energy Dependence of Energy on λ & ν
E = hν
◆ studying blackbody radiation:
objects glow visibly when heated and since: λν = c
ν = c/λ
◆ intensity of radiation emitted varies with λ of
emitted light hc
then: E = ––––
λ
predicted that it would increase continuously
h = Planck’s constant = 6.626 x 10–34 J•s
determined experimentally that it reaches a
maximum ◆ important relationships for electromagnetic radiation:

◆ Planck proposed that the energy radiated by a ν ∝ 1/λ

heated body cannot be continuously variable, but E∝ν
instead emitted in discrete “packets” called quanta. E ∝ 1/λ

Line Spectrum of H Revisited Albert Einstein & the Photoelectric Effect (1905)

The emission of light at photoelectric effect – when a clean metal surface is

specific λ’s corresponds bombarded with electromagnetic radiation,
to specific energies. electrons may be ejected

◆ quantized emission;
not continuous

Determine the energy (in J) of radiation emitted by

threshold frequency is required
H atoms corresponding to the 486 nm (green) line in
ν varies by metal
the emission spectrum.
 Albert Einstein & the Photoelectric Effect (1905) Albert Einstein & the Photoelectric Effect (1905)
If light consists of small particles – photons - we
Einstein explained the photoelectric effect – should be able to quantify their mass:
beams of light behave like a stream of very small
particles if: hc
E = ––– and E = mc2
λ
◆ these particles ≡ photons
Ephoton related to ν, λ hc
application of Planck’s quantized energy then: ––– = mc2
λ

◆ if Ephoton < Ethreshold, no electrons ejected h

or: m = –––
◆ if Ephoton > Ethreshold, electrons are ejected λc

Louis de Broglie & de Broglie Wavelength (1924)

example:
de Broglie believed that if light could behave in ways
consistent with particulate matter, then particulate Determine the de Broglie wavelength of a 1150
matter should exhibit wave-like behavior. kg car traveling at 55.0 mi/h.

We can calculate the wavelength associated with an m = 1150 kg

object of known mass traveling with a specific υ = 55.0 mi/h = 24.6 m/s
velocity.
h = 6.626 x 10–34 J•s = 6.626 x 10–34 kg•m2/s
◆ called the de Broglie wavelength:
h
λ = ––––
mυ
 Wave Interference and Diffraction Patterns Bohr Model of Atomic Structure (1914)
◆ Bohr proposed that electrons can orbit the
nucleus of an atom only in orbits of specific radii
◆ these distances from the nucleus correspond to
specific energies – “allowed energy states”
application of the idea of quantized energy
◆ each orbit is defined by an

integer, n
Work of Einstein, Compton, de Broglie, Davisson & n = 1 orbit is closest to the
nucleus; ground state
Germer, and others helped to establish wave-particle
duality. as n increase, the radius of the
orbit increases, the distance from
the nucleus increases, E increases

Bohr Model of Atomic Structure (1914) Bohr Model of Atomic Structure (1914)
Bohr proposed that electrons can transition from
energy of each “allowed energy state” can be one allowed energy state to another:
determined by the following: ◆ requires that energy be either

absorbed (lower to higher state)

1 )
E = –Rch ( ––– or 1 )
E = –RH ( –––
n2 n2 or
emitted (higher to lower state)
1
E = –2.18 x 10–18 J ( ––– )
n2 ◆ if each energy state is of specific E, then
∆E between states is also specific
occurs at specific λ and ν
1 1
∆E = –2.18 x 10–18 J ( ––– – ––– )
nf 2 ni2
 example:

Calculate the energy (in J)

emitted when an electron
in a hydrogen atom
undergoes a transition
from the n = 4 to n = 2
state.

What wavelength of light

does this correspond to?

Quantum Mechanics & the Heisenberg

Uncertainty Principle (1926 - 1927)

Erwin Schrödinger proposed the quantum

mechanical model: an electron bound to the
nucleus of an atom behaves like a standing wave.

◆ for a standing wave, there must always be a

whole number of ! λ’s

◆ only certain λ’s can correspond to orbits of

specific radii that are stable
 Schrödinger Equation, ψ, & Atomic Orbitals
Heisenberg Uncertainty Principle
The Schrödinger equation can be solved to give an
infinite number of solutions for ψ. It is impossible to know an electron’s position and
velocity simultaneously.
◆ each solution for ψ represents an atomic
orbital (∆x)(∆mv) ≥ h/4π
every atom has an infinite number of
atomic orbitals
◆ each atomic orbital has:
specific size
specific E
specific shape
specific orientation in 3-D space

ψ and ψ2
◆ ψ is the mathematical function that defines an Representations of Where You
atomic orbital Can Expect to Find an Electron:

solution to Schrödinger equation Electron Density Maps

but it has no easily visualized representation

◆ ψ2 indicates the probability of finding an electron

near a point in space
Born interpretation – the probability of
finding an electron at a given position in 3-D
space is proportional to ψ2
 Electron Probability Distribution Radial (or Total) Probability Distribution

Quantum Numbers 2. angular momentum (or Azimuthal) quantum

Each atomic orbital is defined by 3 quantum numbers. number, l

1. principal quantum number, n ◆ identifies the 3-D shape of the orbital

◆ positive integer (1, 2, 3 etc. ! ∞) ◆ can have values from 0 ! n – 1
◆ size and energy of orbital depend primarily on n if n = 1, l = 0
n = 2, l = 0, 1
◆ as n increases: n = 3, l = 0, 1, 2
number of allowed orbitals increases
size of orbitals increases ◆ within a shell (same n value), as l increases,
∴ energy of orbitals increases energy of the orbital increases
◆ n identifies the “shell” of the orbital ◆ l identifies the orbital’s “subshell”
orbitals with the same value of n are said to l = 0 1 2 3 4
be in the same shell subshell s p d f g
3. magnetic quantum number, ml

◆ defines the spatial orientation of the orbital

relative to x, y, z axes
◆ can have values from – l ! l
if l = 0, ml = 0
l = 1, ml = –1, 0, 1
l = 2, ml = –2, –1, 0, 1, 2
l = 3, ml = –3, –2, –1, 0, 1, 2, 3
◆ within a subshell (same l value), orbitals are
degenerate – have the same energy

Relative Energies of Atomic Orbitals s orbitals (l = 0; ml = 0)

◆ spherical
◆ probability of finding an
electron depends on
distance from nucleus,
but not direction
◆ only 1 possible spatial
orientation
◆ 1 s orbital per shell
 p orbitals (l = 1; ml = –1, 0, 1)
◆ dumbbell shaped
◆ 2 identical lobes on opposite sides of nucleus
if lobes lie along x axis, px orbital
if lobes lie along y axis, py orbital
if lobes lie along z axis, pz orbital
◆ nodal plane passing through nucleus;
probability of finding an e– at the nucleus is zero
f orbitals (l = 3; ml = –3, –2, –1, 0, 1, 2, 3)
d orbitals (l = 2; ml = –2, –1, 0, 1, 2)
◆ 4 of the 5 d orbital are clover-leaf or double dumbbell
shaped; 4 lobes
if lobes lie between x and z axes, dxz orbital
if lobes lie between x and y axes, dxy orbital
if lobes lie between y and z axes, dyz orbital
if lobes lie along x and y axes, dx2 – y2 obrital
◆ 5th d orbital has 2 lobes along z axis + donut of e–
density in x-y plane; dz2 obrital