Key Skills in Chemistry II

Workshop 10

Save your spreadsheets at regular intervals

Submit your completed workbooks on Canvas

Higher marks will be awarded for neater and clearer work

Note: Max. Mark = 10/10

All answers to all questions in the script should be typed into the spreadsheets.

You must only submit one workbook, with a separate worksheet for each exercise.

Exercise 1 Wavefunctions for Particle in a Box

An electron is trapped in a box of length 1, i.e. between x = 0 and x = 1. As we have seen

in CHEM260 lectures, the wavefunctions for this are given by

ψn ( x ) = N sin (nπ x ) (1)

where n is an integer quantum number, n = 1, 2, etc…, and N is a normalisation constant.

We can use a spreadsheet to calculate and plot some wavefunctions and look at more
complicated things like overlap integrals, expectation values and to determine the
selection rule for dipole active transitions. In the last part we shall also look at the
eigenfunctions for a harmonic oscillator, and see how the dipole selection rule changes.

Think carefully about how you want to set out the spreadsheet, don’t just charge in typing
formulas. If you don’t know the Excel function for π , look it up online.

1.1 Title the first Worksheet “Particle in a box A” (double click on the tab labelled “Sheet
1” to change the name), and type your name and date at the top of the
worksheet.
CHEM280: Key Skills Workshops 1
 1.2 Make a column of values for the variable x running from 0 to 1 in steps of 0.01 (don’t
start this on row 1 or 2, you will need rows at the top of the spreadsheet for titles
etc.). Then make four columns to calculate the wavefunctions for the first 4 states:
enter the value of the quantum number, n, stored in a cell at the top of the column

( )
and below this calculate ψn = sin nπ x for all the x values using the cell name for the

value of n. (Since we have not determined the normalization yet, we use N = 1.)

1.3 Plot the data as an x,y scatter plot of lines only, no symbols, on the same sheet,
remembering to label the legend, axes etc. In a new column, try increasing the value
of n above 4 to see what the wavefunctions look like.

1.4 Duplicate the worksheet (click on the tab at the bottom with the sheet name, then
hold down the right mouse button to bring up a menu) call it “Particle in a box B”. Edit
the columns containing the ψn values to calculate the probability density distribution
ψn2 (the wavefunction is real, so the square modulus is the same as the square).

€
€ 1.5 Plot the probability density distribution for the first 4 states on this sheet. Try
increasing the value of n for the last column (but don’t take n too high, or you need to
have more points in x to capture all the oscillations) and see what the distribution
looks like. Note that as n goes up the probability starts to oscillate rapidly.

( )
1.6 Now we are going to normalise this wavefunction ψn = N sin nπ x by choosing N so

that the overall probability distribution adds up to 1. To normalise ψ n we require that

2 1
∫ψ n
dx = N 2 ∫ sin2 nπ x dx = 1
( ) (2)
0

€
1
so that N2 = 1 ∫ sin2 nπ x dx
( ) (3)
0

We can approximately evaluate the integral by just adding up all the values of ψn2 in
each column and multiplying by the spacing ∆x (i.e. the integral is approximately:

∆x * Sum(values in ψn2 column) - use the Excel function sum. €

CHEM280: Key Skills

€ Workshops 2
 1
Hence work out the integral ∫ sin2 nπx dx and therefore the normalisation constant
( )
0

N and tabulate the values above the column representing the wavefunctions.

Does N depend on€n?

Looking at the value of N2, give an exact expression, i.e. a formula, for N (not
just a decimal number, which is an approximate answer).

Exercise 2 Expectation values, orthogonality and transitions

2.1 Now we can work out x , the average position of the electron in the box, by

evaluating the mean or expectation value of the position, i.e.

2
x = ∫ ψ * ( x) x ψ ( x) dx = ∫ x ψ ( x) dx
n n n (4)

Duplicate worksheet “Particle in a box B” and rename it “Particle in a box C”, then
delete the
€ graphs, and the sums for the normalization since we don’t need these.

Multiply the formula in each wavefunction column by the exact expression for the
normalization constant, N, i.e. an Excel function. From now on we are only working
with normalized wavefunctions.

[Note, if you have values for ψn2 in your column you need to multiply by N2, if you
have values for ψn you multiply by N.]

Calculate a new column containing (x ψ ) and integrate as in 1.6 to get

2
n x .

Does the mean position of the electron depend on n?

2.2 Orthogonality. Now we will look at the overlap integral of two different wavefunctions
ψn ( x) and ψm ( x) (n and m are just any two values of the quantum number). Copy
worksheet “Particle in a box A” to make a new one and name it “Particle in a box D”.
CHEM280: Key Skills Workshops 3
€ €
 Remember to normalize the wavefunctions. Adapt the worksheet to calculate the
product of two wavefunctions for each x value, i.e. use a new column to contain the
products of entries on the wavefunction columns. Integrate ψn ( x) ψm ( x) (as in 1.6) to
1
get ∫ 0
ψn * ( x) ψm ( x) dx for a few n and m. Verify the integral is zero (on the computer

zero means very small) unless n = m when it is 1 €

(show several examples in your
worksheet, not just one).
€

2.3 Finally we can see if transitions are allowed between different states n and m. We
need to calculate the transition dipole moment ∫ ψ (x ) µ
m x
ψn ( x ) dx (the

eigenfunctions are real not complex). The dipole moment operator µˆ x is just the
product of the charges times their position, so it is proportional to the position, x, of
the electron in the box. If the integral
€
∫ x ψ (x )
m
ψn ( x ) dx

(i.e. integrate the product of x, wavefunction m and wavefunction n where m and n

are different values of the quantum number) is non-zero then a transition is
allowed between the two states n and m. If the integral is zero (note the computer
can’t get zero exactly, just a very small number), the transition is forbidden.

Copy the worksheet “Particle in a box D” to make a new one called “Particle in a

box E”. Adapt it to calculate x ψn x ψm x ( () ( )) (i.e. make a new column that is the

product of entries from 3 other columns, one the values of x).

Integrate ( x ψ ( x ) ψ ( x ))
n m
to get the transition dipole moment and compare the

relative intensities for transitions from n = 1 to m = 2, 3 and 4, and from n = 2 to m =

3 and 4.

Determine and state the selection rule, i.e. along the lines of “transitions only occur
between states where Δn = …” – note it is the allowed transitions you are looking for.

CHEM280: Key Skills Workshops 4

 Exercise 3 The Harmonic Oscillator

From CHEM260, we know that near its minimum of energy a molecular potential is
approximately harmonic, with a potential energy V(x) = − 21 kx 2 where x is the displacement
from the equilibrium bond length x = (r − re ) and k is the force constant of the bond. The

h k
energy levels are given by Ev = (v + 0.5)€!ω in Joules, where !ω = in Joules and µ
2π µ
€
m1m2
is the reduced mass of the molecule µ = .
€ (m1 + m2 )
€
The eigenfunctions of the harmonic oscillator are given by
€
(
ψv = A Ηv ( x ) exp − x 2b0.5 2 )
µk
where A is a normalisation constant, b = and Hv(x) are called Hermite polynomials,
!2

Η 0 ( x) = 1, Η1( x) = 2b0.25 x , Η 2 ( x) = 4b0.5 x 2 − 2 , Η 3 ( x) = 8b0.75 x 3 −12b0.25 x etc.

€
These are complicated, so rather than type it all in, we will start with a spreadsheet that
€ already€has the main formulas.
€ On VITAL go to the
€ Maths Workshops section in Learning
Resources for CHEM280 and download harmonic-start.xlsx. In your original workbook,
open a new worksheet and call it “Harmonic”. Copy and paste the contents of

harmonic-start.xlsx into worksheet Harmonic.

3.1 Complete calculation of the wavefunctions by filling x-values down to +x(max) in

steps of dx. Fill down the wavefunction columns and the Hermite polynomials.
Make plots of the wavefunctions, they are sort of smeared out versions of the particle
in a box wavefunctions (if not you’ve done something wrong).

3.2 Check that the wavefunctions are normalized by integrating (the Excel function
sumsq might be useful).

3.3 Determine the selection rule for dipole transitions by looking at the transition

dipole moments: in new columns calculate the product x ψn x ψm x ( ( ) ( ) ) for m = 0

and n = 1, 2 and 3, then for m = 1, and n = 2 and 3, and finally for m = 2, n = 3. Sum
the data in the columns to get the integrals (don’t forget ×dx). Note that in the units
used here 10-11 is a strong transition, 10-20 or smaller is zero.

CHEM280: Key Skills Workshops 5