I. Considering the molecule given below
where 𝑘 = 0,1,2,3,4,... and a total of 𝑚 = 2𝑘 + 5 atoms in the conjugated chain
including the nitrogen atoms, whereas the hydrogen atoms are excluded,
because they are not part of the conjugated network of bonds. Treat this
molecular system as linear molecule. Answer the following questions by the
application of quantum mechanical particle in a box (PIB) model.
1. How many electron pairs participate in the 𝜋-system of the molecule (when
k=0)?
2. Is the number of 𝜋-electrons equals to the quantum number of the ground
state HOMO? Provide your rationale.
3. Identify 𝑛HOMO and HOMO – LUMO gap with increase of 𝑘. Show that ΔE
is inversely proportional to length (L) of the molecule. Provide a schematic
diagram (a graph) for this inverse relation between ΔE and L.
4. Would there be a value of k for which the molecule loses its HOMO-LUMO
gap (aka the band gap)? Would that be metallic?
5. Can a metallic state be achieved for larger values of k? Provide your
rationale.
6. Do you see a transition from molecule to a crystal for larger values of k?
How would you justify that?
Explanation: The PIB model is frequently used for rationalizing the electronic
spectra of linear chain 𝜋-conjugated molecules. In the application of this
model, one uses the PIB eigenstates (energy levels) to describe the spacing of
the 𝜋 orbitals of conjugated molecules; for example, one would consider
symmetric cyanine molecule (these are also the popular dyes), which is shown
below.
1
where 𝑘 = 0,1,2,3,... and a total of 𝑚 = 2𝑘 + 5 atoms in the conjugated chain
including the nitrogen atoms, whereas the hydrogen atoms are excluded,
because they are not part of the conjugated network of bonds.
Usually in the experiments of UV-Vis spectroscopy, the longest wavelength
absorption resulting from a transition from the electronic ground state to the
first excited state can observed.
The wavelength of light absorbed by the molecule as it transitions into the
excited state is related to the energy difference Δ𝐸 between the excited state
and the ground state by Planck’s equation
The first electronic excited state is assigned to a transition from the highest
occupied molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO).
Important: Most of the times, for 𝜋-conjugated molecules, the HOMO is a 𝜋
orbital, and the LUMO is also a 𝜋 orbital and often labeled 𝜋∗ (antibonding) to
indicate that it is not occupied in the ground state. For 𝜋-conjugated chains, the
𝜋-type orbitals are the ones representing the frontier molecular orbitals (FMO),
the HOMO, LUMO, and the few levels above and below these MOs.
The energies of the 𝜋 orbitals are then identified with the energy levels of the
PIB, the linear extension of the conjugated 𝜋 chain corresponds to the 𝑥-axis of
the PIB model (the box length L), and the box boundaries roughly correspond
to the terminal groups of the molecule (see the given structure of the molecule).
2
The number of electron pairs participates in the 𝜋 system is equal to the quantum
number of the ground state HOMO. It is important to know that for the cyanine
molecule given in the question, there are 𝑛HOMO = 𝑘 + 3 electron pairs. This
values of 𝑛HOMO increases as the box length increases with 𝑘 .
The excitation energy is then approximated by the equation given below: Note
that 𝑛LUMO = 𝑛HOMO + 1
Schematic energy level diagram indicating ground and first excited state
3
Assume that all C–C bond lengths are equal roughly equal to 144 pm.
Assume that the length of –CH=CH– unit is 250 pm (a). And, assume a length
of 570 pm (b) for =CH– with NR2 end members added together. That would
lead to a generic expression as
L = a(k+1)+b pm
From the expression above, one can see that ΔE is inversely proportional to
length (L) of the molecule. In other words wavelength (λ) increases with the
molecular length. In turn, in other words, the HOMO-LUMO gap decreases
with increase of the length of the molecule.
For
example:
See
the
Table
below:
k
𝑛 ≈λ
HOMO
0
3
300
1
4
400
2
5
500
3
6
600
A schematic sketch of how the HOMO-LUMO gap decreases with increase of
L or the value of k:
4
One can make a neat table or a graph for the system given above. The energy
levels of HOMO and LUMO and the difference are (ΔE) shown here in two
graphs. Note that the energy is scaled to 105 in the units of (h2/2m).
II.
Construct molecular orbital energy level diagram for H2O in its ground state
using fragment molecular orbitals.
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III.
3. Construct molecular orbital energy level diagrams for NH3 when it is
trigonal planar and pyramidal molecular arrangements. Notice the differences
in the HOMO and LUMO levels in each case.
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