CH301 Summary of Chapter 12 - Study Notes and Study Guide by KaYee Tong.

If this helps you a lot, give me a hug.

Some content are copied off good websites and some from Mccord’s lecture.
Random stuff: my philosophy: If shit happens, it isn’t shit.
Electromagnetic Radiation.
A form of energy our eyes only detect a tiny portions of; various modern detectors ‘see’ a much
wider range. Isaac Newton sent white light through a prism - noted its a mix of many different
colors. Light behaves in many experiments as if it were a wave. Waves have known properties.
Properties of Waves - specifically Light
Waves have three linked components:
Specifically for electromagnetic waves:
Wavelength
λ,
speed c
frequency ν
For electromagnetic radiation, c = ν λ
c = speed of light = 3 x 108 m/s

What is ‘waving’? (Fig 12.1)

The strength (amplitude) of both Electrical and Magnetic Fields varies: There are two waves, one
at right angles to the other, both traveling in the same direction.

The Electromagnetic Spectrum (Fig 12.3)

“Light” is just a tiny section of the entire E-M spectrum. Extends in both directions.

Example: What is the frequency of green light, wavelength 520 nm?

The Electromagnetic Spectrum: what you need to know: (Fig 12.2, 12.3)
In addition to being able to use c = νλ, you should be able to determine for different given types
of electromagnetic radiation:
Which has the longer (bigger) wavelength?
Which has the shorter (smaller) wavelength?
Which has the highest (greatest, largest) frequency?
Which has the lowest (smallest) frequency?
Know the Visible range: 400nm-700nm (0.4-0.7μm)
Know the names of the others (not the wavelength ranges)
Know the order: (inc. wavelength) : Gamma rays, X rays, UV, Visible, IR, Microwave, Radio
Know the short wavelength (higher frequency) end of the visible is BLUER
Know the long wavelength (lower frequency) end of the visible is REDDER

Blackbody Radiation (Fig 12.4)

All objects above absolute zero emit some E-M radiation. ‘Blackbody’ - an object that can absorb
or emit any wavelength of light with equal efficiency. Blackbodies emit radiation over all
wavelengths but the relative amounts of each wavelength will vary depending on the temperature.
At room temperature very little radiation is emitted at very high or low wavelengths, most will be
emitted in the infrared.
What happens to the coil on your electric stove, or a light bulb wire as you turn on the power.?
Hot objects appear to glow (incandescence). As temperature increases: we sense more heat (IR)
coming from the object. The object glows dull red, then orange, then yellow, then white.
The distribution is a series of lopsided curves of emitted energy intensity vs. wavelength. For
each temperature, there is a peak.
Blackbody Radiation and the UV Catastrophe
Theoreticians could NOT reproduce this experimental data. The classical mechanics model
worked poorly at long wavelengths AND predicted infinite values at short wavelengths!
“The ultraviolet catastrophe” : Any body above absolute zero would be emitting vast amounts of
UV, gamma and X-rays! The solution came with a bold jump: the assumption that energy was
QUANTIZED. Only specific amounts of energy can be absorbed or emitted by matter.

Quantized Radiation
1900: Max Planck explains the emission of blackbody radiation by proposing that energy could
only be absorbed or emitted by matter in discrete “quantized” amounts, corresponding to
“packets” of energy.
The energy of a packet of light energy is related to its frequency: E = h ν where h = 6.6 x10-34J.s
Cool bodies do not possess enough energy to oscillate at high frequencies so they cannot emit
UV, gamma and X-rays! This theory fits experimental data. Another useful equation: E = (hc)/λ
What do you notice about the size of h??

More quantization evidence: The Photoelectric Effect

Experimental Data:
Shine light on a metal surface and electrons are ejected.
But ONLY if the light’s frequency is above a certain value, ν0.
For light with a frequency above ν0 : Number of electrons ejected is proportional to intensity.
If the frequency of the light used is varied (e.g. using filters):
The kinetic energy of the ejected electrons increases linearly with the frequency of the light used.

Einstein Explains The Photoelectric Effect (Fig 12.8, 12.9)

Light consists of particles: photons - bundles of energy (E = hν).
A specific amount of energy Φ is needed to remove the electron from the metal atom.
This is the work function. Photons must have MORE energy than Φ .
The remaining energy shows up as kinetic (moving) energy of the electron:
KE = ½ mve2 = hν - Φ Note Φ = hν0 and for many metals, ν0 is in the UV.

Evidence for Wavelike Nature of Light (image from Wikipedia - under 'Young's slits')
19th century: Thomas Young shows light behaves like waves, using a double-slit experiment. The
interference pattern produced was exactly that which would be made on a larger scale by water
waves. Waves interfere when they pass through one another: See Fig 12.7:
CONSTRUCTIVE INTERFERENCE: Peaks, troughs coincide: Amplitudes ADD
DESTRUCTIVE INTERFERENCE: One wave’s peak & other’s trough coincide: Amplitudes SUBTRACT

What is Light ?
Is light a wave or a particle? There is evidence for BOTH views of light!!
1924: Prince Lois de Broglie suggests: ALL matter has a wavelike aspect to it.
It also followed that: ALL waves can behave like they are particles.
This is called WAVE PARTICLE DUALITY. Light and matter are BOTH waves AND particles!
The result we get (wave or particle) depends on how we construct an experiment!

de Broglie’s Equation: λ= h/p or λ = h / mv

Remember the size of the value of h?
The effect isn’t seen on everyday objects - they are so massive that the wavelength is infinitely
small. For particles of light, or small bits of matter like electrons, the effect is measurable.
Diffraction Patterns (Fig 12.7)
.Caused by waves being scattered by points spaced at similar distances to the wavelength of the
wave. If l is known, the spacing can be found (or reverse) .
ALSO observed with electrons, neutrons etc!

ATOMIC SPECTRA (Fig 12.8 and http://astro.u-strasbg.fr/~koppen/discharge/ )

EMISSION spectrum:
Pass an electric current through a pure gas sample
Send emitted light through a prism:
ONLY certain specific wavelengths are emitted: see a series of bright lines on a dark background.
ABSORPTION spectrum:
Pass white light through sample of pure gas being exited by an electric current.
Send any light that passes sample through a prism:
ONLY certain specific wavelengths are absorbed: see a continuous spectra with dark lines.

The wavelength of the dark lines in an absorption spectra and the bright lines in an emission
spectra are in the same places. EVERY ELEMENT has a UNIQUE set of lines!
We can use this to identify elements present in a sample

Implications of emission spectra (Fig 12.9)

Electrons in hydrogen atoms can only have specific energies because only specific changes in
energy (ΔE) are permitted. ΔE = hν = hc/λ

Bohr model of the Hydrogen Atom: (Fig 12.10): A minature “solar system”
•The closer the orbit to the nucleus, the lower its energy.
• ONLY certain orbits are allowed.
• To move an electron to an orbit further out, it must gain the equivalent extra amount of energy.
•The amount of energy is specific to the levels involved and is quantized –hence only certain
colors are seen in the spectra.
This only worked for very simple species like H, He2+, Li3+ ..with one electron.
Classical physics: this model is unstable. Planets aren’t charged ; the electron and nucleus are!

Rydberg Equation
ν=
c ⎛ 1 1 ⎞
Various sets of lines in Hydrogen’s spectrum were = R⎜ 2 ­ 2 ⎜ n1 < n 2
found by Balmer (visible), Lyman (UV) and others, λ ⎝ n1 n2 ⎠
and were named after them. Everyone had their
own equation to explain the lines: R = Rydberg constant = 3.29 × 1015 Hz
Johann Rydberg put it all together..

NOTE: This is the frequency of an emission line

so if we insert this into ΔE = hν we get the DIFFERENCE in energy between two different
energy levels , n1 and n2.
For the BALMER series of lines, n1 = 2 and n2 = 3,4, 5,..
For the LYMAN series of lines, n1 = 1 and n2 = 2, 3, 4, 5
Allowed energies for a One electron atom: (H, He+, C5+, Te51+ etc!!)
Starting from the Rydberg equation, multiplying R by h and adding in a term to allow for different
nuclear charges we get:
En = -2.178 x 10-18J x (Z2/ n2)
n = the level the electron is in Z = atomic number of the atom
Note this means that the spectra of any one-electron atom* can be predicted.
Add another electron, and it goes wrong!

Limitations of Bohrs model

Based on classical mechanics (from Isaac Newton) Works fine for cars, planets, macroscopic
objects. Only works for one electron atoms and requires assumptions (special stable orbits) that
cannot be justified in classical mechanics. Does not work for many electron atoms
Bohr tried to extend model with ellipses but failed.

See Fig 12.12: deBroglie tried to tweak Bohrs model to view the electron in an orbit as a standing
wave... ...does explain the “special orbits”. Still doesn’t explain more complex spectra. Electrons
do NOT move in circular orbits!.

Quantum (Wave) Mechanics

Erwin Schrodinger replaced the classical trajectory of a particle with a mathematical equation
called a WAVEFUNCTION (Ψ). The value of Ψ varies depending on position.
At its simplest, this can be written: H Ψ = E Ψ
E = energy of the particle H = Hamiltonian : an energy operator (some math instructions).
BUT WHAT IS Ψ ???

Heisenberg’s Uncertainty Principle

We can easily determine the position of a macroscopic object (a big particle), even if it is moving.
The position of a wave is not so easy .. where does it start and end? The motion of a wave can
be determined. Now consider a photon or an electron...
We CANNOT determine BOTH the POSITION AND the MOMENTUM possessed by a particle to
extreme precision.
As one becomes more accurate the other becomes less so.
If position error is Δx, and momentum error is Δp, then Δp Δx = h-bar /2 = h/4π (h-bar is h/2π)
This comes from the mathematics of Quantum Mechanics. Here’s a simpler view:
A macroscopic measurement can be easily done so that we do not influence the object we are
measuring. Bounce laser light off the Moon and measure its return time - to get the Moon’s
distance very accurately. The Moon did not recoil!
BUT: Hit an electron with the laser, we knock it about and would not be able to tell what motion
was due to the laser and what was due to its original motion.
How to interpret Ψ
Max Born: The value of the square of Ψ (i.e., Ψ2) for some point in space is proportional to the
probability* of finding the particle in that region of space. If we square any function, certain things
happen. For example, if f(x) at some value of x is negative, then [f(x)]2 has to be positive.
If Ψ2 = zero at some region we say we are at a NODE. The particle will NEVER be found there.
*Probability: For a good chance of winning, you look for a game with a high probability of your
desired result (e.g. lottery number) occurring.

The Schrodinger Equation

A simple version of the energy operator would be: - h2 d2 ψ + V ψ = E ψ
2m dx2
We write an H for the physics of our situation.
H has terms for different types of energy (KE and PE) that exist for the particular system.
This is a differential equation, so, there are solutions ! Equations of the form “Ψ = ….”

Solutions of the Schrodinger Equation

Valid solutions are those which make sense mathematically (don’t become infinite!)
Also: They also have smooth variations in their value (no instantaneous jumps from one region to
the next). They can also only have one value at each point in space.
Lets see how to solve the simplest possible situation.....BEFORE we do this for an electron!!

Simple Application of Schrodinger Equation:

The Particle in a 1-Dimensional Box (Fig 12.13)
1. Particle, mass m,
2. Can only move in 1-D (the x-dimension).
3. Rigid walls, distance L apart either side of the particle.
4. While within the walls, particle has zero potential energy.
5. Particle CANNOT exist outside of the walls.
What can we say so far? Ψ = 0 at the two walls, since Ψ2 = 0 also. What about in between?
We cannot have this sketch below: Why not? (see above).

Here is a possible solution: It works a lot like a guitar string…nice sine curves!
CH301 Chapter 12 Notes: Part 2:

Solution to the Schrödinger Equation: The Particle in a 1-Dimensional Box

Ψn(x) = (2/L)1/2 sin(nΠx/L)
This equation summarizes a set of n sinusoidal curves: Ψ1 , Ψ2 , Ψ3 , Ψ4 , Ψ5………

Allowed energies of a particle in a 1-D box:

Each solution has its own specific energy: En = n2h2
E1 , E2 , E3 , E4 , E5…………. 8mL2

n is known as a QUANTUM NUMBER. In this case, n is a positive, nonzero integer.

Any other value of n would not work - it would not be a solution to the Schrödinger equation!
What happens to E for any value of n if we let m or L increase?

Figure 12.14 shows the energies, wavefunctions and square of the wavefunctions for the
first three solutions (n=1, n=2, n=3). In class we'll discuss the third one in detail.

Interpreting the solution for a particle in a 1-D box (Figure 12.14):

Each wavefunction is equal to zero at x = 0 and x = L (as required by the boundary conditions)
Note the energy level ‘ladder’ -- QUANTIZED energies.

Remember Ψ2 gives the idea of WHERE the particle is likely to be!

How does this compare to what you would expect for a macroscopic object?

What do I need to know?

Be able to sketch and interpret any of the first 8 or so solutions: e.g., Ψ3, or Ψ22 ….
Where are the NODES. What is a Node?
Where will you be most/least likely to find the particle? What does Ψ2 mean?

Energy needed to jump from one level to another: (Figure 12.14)

We can calculate the energy to go from Ψn1 to level Ψn2 : ∆E = (n22-n12) h2
where n1 and n2 are two different values of n. We see that the gaps 8mL2
themselves, ∆E, are also inversely proportional to L (actually L2) and m.

Example: A ball mass 0.5g in a 1D box 2m long: What energy is needed to go from n=4 to n=7 ?

Zero Point Energy: Quantum Weirdness

What about n=0? Ψ0 does NOT exist! The smallest allowed value of n is 1. The energy of a
particle in a 1-D box can never be zero! To calculate ZPE use n=1 and your values of m and L.
What do I need to know?
Be able to sketch the energy level diagram and interpret it: (what happens as we change n,L)
Be able to do calculations of values of E for a particular wavefunction given n,m,L
Be able to calculate ∆E for a particular wavefunction given two values of n, and m,L
Be able to calculate the ZPE if given m,L (obviously you know what n is!!! )
Also the sort of qualitative examples we’ve done.
Always remember that you should get very tiny numbers if your object is macroscopic. Why?

The Schrodinger Equation for the H atom

We write the Schrodinger equation with terms for KE and PE; find the solutions (Ψ), and feed
those back in to solve for E:
The allowed energies are: (Schrodinger did this)
En = -hR where R = mee4 and n=1,2,3….
n2 8h3ε02
We have agreement with experiment!
E is proportional to R/n2 …and we get a value for R.
The value agrees with the experimental one!

YOU DO NOT NEED TO MEMORIZE THE SOLUTIONS!!!!

For the atom, these solutions (wavefunctions) are called ORBITALS.

WHAT DO I NEED TO KNOW ABOUT THAT SCHRODINGER DUDE’S EQUATION???

How many of each type (yes they get categorized), What they look like (plotted)
How many of each type exist
How they are ordered (in terms of energy)
What the shape means in terms of where the electrons are
(remember Ψ is a probability density - how likely we are to find that electron in that region)

The solutions are more complex than a 1-D or 3-D box! They are shown in Table 12.1
Notes: Atoms are spherical, so the math is done using polar* (r, θ, φ ) coordinates, not cartesian
(x,y,z) coordinates. The orbitals are solved two parts: Radial, R, and Angular, Y.
a0 (the Bohr radius) is a bunch of constants. a0 = ~52.9pm - roughly, the size of an H atom!
ALL YOU HAVE TO DO IS LEARN THEIR SHAPES AND THEIR QUANTUM NUMBERS!!
*Polar coordinates are similar to GPS coordinates: latitude, longitude and height above sea level.

The Four Quantum Numbers and their Rules:

1.The PRINCIPAL quantum number, n. Describes the main energy level and approximate
nuclear distance. Sometimes referred to as a shell; it links back to the n shown by Bohr, Balmer
and others for the classical model. Rule: n may have any positive integer value from 1 to infinite.
2.The ANGULAR MOMENTUM (think of an ice skater) quantum number, l. Describes the shape
in space occupied by the electron. For each value of n, there are sublevels or subshells which
each have a certain shape. Rule: l may have any integral number from 0 up to and including n-1.
3.The MAGNETIC quantum number, ml. Describes the specific orbital within a subshell, each of
which have different spatial orientations. The number of values of ml gives you the number of
orbitals for a given subshell. Rule: ml may have any integral value for –l through 0 to +l.
4.The SPIN quantum number, ms. Refers to the spin of an electron and the orientation of the
magnetic field produced by this spin (a simplistic model being the electron spins like a top). Rule:
for ANY value of the previous three quantum numbers, ms may have two values: + ½ or – ½.

4th quantum number? To explain the tiny deviations of predicted spectral lines from experimental
ones, a 4th one was needed – the spin quantum number ms. It was proposed by Goudsmit and
Uhlenbeck. Experimental evidence of electron “spin” was first detected by Stern and Gerlach.
Blackbody Radiation and the UV Catastrophe
Theoreticians could NOT reproduce this experimental data. The classical mechanics model
worked poorly at long wavelengths AND predicted infinite values at short wavelengths!
“The ultraviolet catastrophe” : Any body above absolute zero would be emitting vast amounts of
UV, gamma and X-rays! The solution came with a bold jump: the assumption that energy was
QUANTIZED. Only specific amounts of energy can be absorbed or emitted by matter.

Quantized Radiation
1900: Max Planck explains the emission of blackbody radiation by proposing that energy could
only be absorbed or emitted by matter in discrete “quantized” amounts, corresponding to
“packets” of energy.
The energy of a packet of light energy is related to its frequency: E = h ν where h = 6.6 x10-34J.s
Cool bodies do not possess enough energy to oscillate at high frequencies so they cannot emit
UV, gamma and X-rays! This theory fits experimental data. Another useful equation: E = (hc)/λ
What do you notice about the size of h??

Example: What is the energy of a single quanta of green light, wavelength 520nm?

More quantization evidence: The Photoelectric Effect

Experimental Data:
Shine light on a metal surface and electrons are ejected.
But ONLY if the light’s frequency is above a certain value, ν0.
For light with a frequency above ν0 : Number of electrons ejected is proportional to intensity.
If the frequency of the light used is varied (e.g. using filters):
The kinetic energy of the ejected electrons increases linearly with the frequency of the light used.

Einstein Explains The Photoelectric Effect (Fig 12.8, 12.9)

Light consists of particles: photons - bundles of energy (E = hν).
A specific amount of energy Φ is needed to remove the electron from the metal atom.
This is the work function. Photons must have MORE energy than Φ .
The remaining energy shows up as kinetic (moving) energy of the electron:
KE = ½ mve2 = hν - Φ Note Φ = hν0 and for many metals, ν0 is in the UV.

Evidence for Wavelike Nature of Light (image from Wikipedia - under 'Young's slits')
19th century: Thomas Young shows light behaves like waves, using a double-slit experiment. The
interference pattern produced was exactly that which would be made on a larger scale by water
waves. Waves interfere when they pass through one another: See Fig 12.7:
CONSTRUCTIVE INTERFERENCE: Peaks, troughs coincide: Amplitudes ADD
DESTRUCTIVE INTERFERENCE: One wave’s peak & other’s trough coincide: Amplitudes SUBTRACT

What is Light ?
Is light a wave or a particle? There is evidence for BOTH views of light!!
1924: Prince Lois de Broglie suggests: ALL matter has a wavelike aspect to it.
It also followed that: ALL waves can behave like they are particles.
This is called WAVE PARTICLE DUALITY. Light and matter are BOTH waves AND particles!
The result we get (wave or particle) depends on how we construct an experiment!

de Broglie’s Equation: λ= h/p or λ = h / mv

Remember the size of the value of h?
The effect isn’t seen on everyday objects - they are so massive that the wavelength is infinitely
small. For particles of light, or small bits of matter like electrons, the effect is measurable.
Diffraction Patterns (Fig 12.7)
Caused by waves being scattered by points spaced at similar distances to the wavelength of the
wave. If l is known, the spacing can be found (or reverse) .
ALSO observed with electrons, neutrons etc!

ATOMIC SPECTRA (Fig 12.8 )

EMISSION spectrum:
Pass an electric current through a pure gas sample
Send emitted light through a prism:
ONLY certain specific wavelengths are emitted: see a series of bright lines on a dark background.
ABSORPTION spectrum:
Pass white light through sample of pure gas being exited by an electric current.
Send any light that passes sample through a prism:
ONLY certain specific wavelengths are absorbed: see a continuous spectra with dark lines.

The wavelength of the dark lines in an absorption spectra and the bright lines in an emission
spectra are in the same places. EVERY ELEMENT has a UNIQUE set of lines!
We can use this to identify elements present in a sample

Implications of emission spectra (Fig 12.9)

Electrons in hydrogen atoms can only have specific energies because only specific changes in
energy (ΔE) are permitted. ΔE = hν = hc/λ

Bohr model of the Hydrogen Atom: (Fig 12.10): A minature “solar system”
•The closer the orbit to the nucleus, the lower its energy.
• ONLY certain orbits are allowed.
• To move an electron to an orbit further out, it must gain the equivalent extra amount of energy.
•The amount of energy is specific to the levels involved and is quantized –hence only certain
colors are seen in the spectra.
This only worked for very simple species like H, He2+, Li3+ ..with one electron.
Classical physics: this model is unstable. Planets aren’t charged ; the electron and nucleus are!

Rydberg Equation
ν=
c ⎛ 1 1 ⎞
Various sets of lines in Hydrogen’s spectrum were = R⎜ 2 ­ 2 ⎜ n1 < n 2
found by Balmer (visible), Lyman (UV) and others, λ ⎝ n1 n2 ⎠
and were named after them. Everyone had their
own equation to explain the lines: R = Rydberg constant = 3.29 × 1015 Hz
Johann Rydberg put it all together..

NOTE: This is the frequency of an emission line

so if we insert this into ΔE = hν we get the DIFFERENCE in energy between two different
energy levels , n1 and n2.
For the BALMER series of lines, n1 = 2 and n2 = 3,4, 5,..
For the LYMAN series of lines, n1 = 1 and n2 = 2, 3, 4, 5
Allowed energies for a One electron atom: (H, He+, C5+, Te51+ etc!!)
Starting from the Rydberg equation, multiplying R by h and adding in a term to allow for different
nuclear charges we get:
En = -2.178 x 10-18J x (Z2/ n2)
n = the level the electron is in Z = atomic number of the atom
Note this means that the spectra of any one-electron atom* can be predicted.
Add another electron, and it goes wrong!

Example: Find the λ of the second emission line in the Balmer series. (See Fig 12.10, the green
arrow) Look at the diagram: which two energy levels is this transition going between?

Limitations of Bohrs model

Based on classical mechanics (from Isaac Newton) Works fine for cars, planets, macroscopic
objects. Only works for one electron atoms and requires assumptions (special stable orbits) that
cannot be justified in classical mechanics. Does not work for many electron atoms
Bohr tried to extend model with ellipses but failed.

See Fig 12.12: deBroglie tried to tweak Bohrs model to view the electron in an orbit as a standing
wave... ...does explain the “special orbits”. Still doesn’t explain more complex spectra. Electrons
do NOT move in circular orbits!.

Quantum (Wave) Mechanics

Erwin Schrodinger replaced the classical trajectory of a particle with a mathematical equation
called a WAVEFUNCTION (Ψ). The value of Ψ varies depending on position.
At its simplest, this can be written: H Ψ = E Ψ
E = energy of the particle H = Hamiltonian : an energy operator (some math instructions).
BUT WHAT IS Ψ ???

Heisenberg’s Uncertainty Principle

We can easily determine the position of a macroscopic object (a big particle), even if it is moving.
The position of a wave is not so easy .. where does it start and end? The motion of a wave can
be determined. Now consider a photon or an electron...
We CANNOT determine BOTH the POSITION AND the MOMENTUM possessed by a particle to
extreme precision.
As one becomes more accurate the other becomes less so.
If position error is Δx, and momentum error is Δp, then Δp Δx = h-bar /2 = h/4π (h-bar is h/2π)
This comes from the mathematics of Quantum Mechanics. Here’s a simpler view:
A macroscopic measurement can be easily done so that we do not influence the object we are
measuring. Bounce laser light off the Moon and measure its return time - to get the Moon’s
distance very accurately. The Moon did not recoil!
BUT: Hit an electron with the laser, we knock it about and would not be able to tell what motion
was due to the laser and what was due to its original motion.

Example 1: Imagine we know that electron is moving in an atom at half the speed of light with an
error of 0.5%, what is the error in its position?

Example 2: Imagine we know that a 0.22 caliber bullet of mass 3.89 x 10-3 kg is moving at 395
m/s with an error of with an error of 0.5%, what is the error in its position?
How to interpret Ψ
Max Born: The value of the square of Ψ (i.e., Ψ2) for some point in space is proportional to the
probability* of finding the particle in that region of space. If we square any function, certain things
happen. For example, if f(x) at some value of x is negative, then [f(x)]2 has to be positive.
If Ψ2 = zero at some region we say we are at a NODE. The particle will NEVER be found there.
*Probability: For a good chance of winning, you look for a game with a high probability of your
desired result (e.g. lottery number) occurring.

The Schrodinger Equation

A simple version of the energy operator would be: - h2 d2 ψ + V ψ = E ψ
2m dx2
We write an H for the physics of our situation.
H has terms for different types of energy (KE and PE) that exist for the particular system.
This is a differential equation, so, there are solutions ! Equations of the form “Ψ = ….”

Solutions of the Schrodinger Equation

Valid solutions are those which make sense mathematically (don’t become infinite!)
Also: They also have smooth variations in their value (no instantaneous jumps from one region to
the next). They can also only have one value at each point in space.
Lets see how to solve the simplest possible situation.....BEFORE we do this for an electron!!

Simple Application of Schrodinger Equation:

The Particle in a 1-Dimensional Box (Fig 12.13)
1. Particle, mass m,
2. Can only move in 1-D (the x-dimension).
3. Rigid walls, distance L apart either side of the particle.
4. While within the walls, particle has zero potential energy.
5. Particle CANNOT exist outside of the walls.
What can we say so far? Ψ = 0 at the two walls, since Ψ2 = 0 also. What about in between?
We cannot have this sketch below: Why not? (see above).

Here is a possible solution: It works a lot like a guitar string…nice sine curves!
CH301 Chapter 12 Notes: Part 2:

Solution to the Schrödinger Equation: The Particle in a 1-Dimensional Box

Ψn(x) = (2/L)1/2 sin(nΠx/L)
This equation summarizes a set of n sinusoidal curves: Ψ1 , Ψ2 , Ψ3 , Ψ4 , Ψ5………

Allowed energies of a particle in a 1-D box:

Each solution has its own specific energy: En = n2h2
E1 , E2 , E3 , E4 , E5…………. 8mL2

n is known as a QUANTUM NUMBER. In this case, n is a positive, nonzero integer.

Any other value of n would not work - it would not be a solution to the Schrödinger equation!
What happens to E for any value of n if we let m or L increase?

Figure 12.14 shows the energies, wavefunctions and square of the wavefunctions for the
first three solutions (n=1, n=2, n=3). In class we'll discuss the third one in detail.

Interpreting the solution for a particle in a 1-D box (Figure 12.14):

Each wavefunction is equal to zero at x = 0 and x = L (as required by the boundary conditions)
Note the energy level ‘ladder’ -- QUANTIZED energies.
Sketch the plots of to Ψ3 and Ψ32 here and add the comments/notes:

Remember Ψ2 gives the idea of WHERE the particle is likely to be!

How does this compare to what you would expect for a macroscopic object?

What do I need to know?

Be able to sketch and interpret any of the first 8 or so solutions: e.g., Ψ3, or Ψ22 ….
Where are the NODES. What is a Node?
Where will you be most/least likely to find the particle? What does Ψ2 mean?

Energy needed to jump from one level to another: (Figure 12.14)

We can calculate the energy to go from Ψn1 to level Ψn2 : ∆E = (n22-n12) h2
where n1 and n2 are two different values of n. We see that the gaps 8mL2
themselves, ∆E, are also inversely proportional to L (actually L2) and m.

Example: A ball mass 0.5g in a 1D box 2m long: What energy is needed to go from n=4 to n=7 ?

Zero Point Energy: Quantum Weirdness

What about n=0? Ψ0 does NOT exist! The smallest allowed value of n is 1. The energy of a
particle in a 1-D box can never be zero! To calculate ZPE use n=1 and your values of m and L.
What do I need to know?
Be able to sketch the energy level diagram and interpret it: (what happens as we change n,L)
Be able to do calculations of values of E for a particular wavefunction given n,m,L
Be able to calculate ∆E for a particular wavefunction given two values of n, and m,L
Be able to calculate the ZPE if given m,L (obviously you know what n is!!! )
Also the sort of qualitative examples we’ve done.
Always remember that you should get very tiny numbers if your object is macroscopic. Why?

The Schrodinger Equation for the H atom

We write the Schrodinger equation with terms for KE and PE; find the solutions (Ψ), and feed
those back in to solve for E:
The allowed energies are: (Schrodinger did this)
En = -hR where R = mee4 and n=1,2,3….
n2 8h3ε02
We have agreement with experiment!
E is proportional to R/n2 …and we get a value for R.
The value agrees with the experimental one!

YOU DO NOT NEED TO MEMORIZE THE SOLUTIONS!!!!

For the atom, these solutions (wavefunctions) are called ORBITALS. Why?

WHAT DO I NEED TO KNOW???

How many of each type (yes they get categorized),
What they look like (plotted)
How many of each type exist
How they are ordered (in terms of energy)
What the shape means in terms of where the electrons are
(remember Ψ is a probability density - how likely we are to find that electron in that region)

The solutions are more complex than a 1-D or 3-D box! They are shown in Table 12.1
Notes: Atoms are spherical, so the math is done using polar* (r, θ, φ ) coordinates, not cartesian
(x,y,z) coordinates. The orbitals are solved two parts: Radial, R, and Angular, Y.
a0 (the Bohr radius) is a bunch of constants. a0 = ~52.9pm - roughly, the size of an H atom!
*Polar coordinates are similar to GPS coordinates: latitude, longitude and height above sea level.

The Four Quantum Numbers and their Rules:

1.The PRINCIPAL quantum number, n. Describes the main energy level and approximate
nuclear distance. Sometimes referred to as a shell; it links back to the n shown by Bohr, Balmer
and others for the classical model. Rule: n may have any positive integer value from 1 to infinite.
2.The ANGULAR MOMENTUM (think of an ice skater) quantum number, l. Describes the shape
in space occupied by the electron. For each value of n, there are sublevels or subshells which
each have a certain shape. Rule: l may have any integral number from 0 up to and including n-1.
3.The MAGNETIC quantum number, ml. Describes the specific orbital within a subshell, each of
which have different spatial orientations. The number of values of ml gives you the number of
orbitals for a given subshell. Rule: ml may have any integral value for –l through 0 to +l.
4.The SPIN quantum number, ms. Refers to the spin of an electron and the orientation of the
magnetic field produced by this spin (a simplistic model being the electron spins like a top). Rule:
for ANY value of the previous three quantum numbers, ms may have two values: + ½ or – ½.

4th quantum number? To explain the tiny deviations of predicted spectral lines from experimental
ones, a 4th one was needed – the spin quantum number ms. It was proposed by Goudsmit and
Uhlenbeck. Experimental evidence of electron “spin” was first detected by Stern and Gerlach.
Note: Remember the SI Unit conversions too!