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1. LCAO-MO for
In class, we discussed the MO picture of and found simple solutions for the
energies of the σ 2 and σ∗ orbitals in terms of a few integrals. After significant effort,
these integrals can all be worked out:

A. Plot (rough sketch is OK) these functions as a function of the distance, R, between the two
hydrogen nuclei. Which terms decay most quickly with distance? Note that ε is the average
energy of a 1s electron on hydrogen atom A. Why is this energy not exactly equal to the
energy of a hydrogen 1s electron?
B. Plot the energies of the σ and σ∗ orbitals as a function of R. What is the equilibrium
bond length for H+ at this level of approximation? What is the binding energy? Compare
these to the 2 experimental values of 1.06 ˚A and 2.8 eV , respectively. How does the
sum of the MO energies, E0 + E0 vary with distance?

Solution:

The one-electron MO energy eigenvalues obtained by solving the variational problem

are
 These energies (minus the energy of the 1s electron at infinite separation) are plotted as
a function of R in Figure 3.

The equilibrium bond length for H+ in this model is found by finding the minimum of Eσ(R).
Using 2 the above expressions and finding the root of the equation dEσ/dR = 0 (must be
done numerically, e.g. with Mathematica’s FindRoot), yields
C. In other chemistry classes, you may have been taught that the strength of a chemical
bond is proportional to the overlap of the atomic orbitals involved. Based on your results
above, how accurate is this approximation for ? When does it break down?

Solution:

small overlap (S < 0.3), the binding energy is indeed roughly proportional to S.
However, this intuitive idea completely breaks down for S > 0.3. The reason is that the
overlap in H+ 2 is correlated with the internuclear distance, and so repulsive effects
are built into the overlap dependence. In general, all else being equal, we still expect
binding energy to scale roughly with increasing overlap.
2. Matrix Mechanics

In class we discussed matrix mechanics, which we will use increasingly often in the
remainder of the course. The following problems provide practice in the mechanics of the
use of matrix notation. Suppose ψ and φ are wavefunctions composed of a linear
combination of three orthonormal basis functions ψ1, ψ2, and ψ3:

A. How would we express ψ and φ in matrix mechanics? That is, what are the vectors ψ
and φ?

Solution:

Given the orthonormal functions {ψ1, ψ2, ψ3}, we define the following two
wavefunctions:

In vector notation, the two wavefunctions are represented by column vectors. Each
element of the vector corresponds to the coefficient of the basis function.
 B. What are ψ† and φ†?

C. Normalize ψ and φ.

Applying normalization to our two wavefunctions yields

D. Compute the inner products ψ† · φ and φ†ψ. Do you notice any relationship between
these two numbers?
Solution:

The inner products of the two wavefunctions are

We note that in general, ψ†φ = (φ†ψ)∗.

E. Are ψ and φ orthogonal?

Solution:
Two wavefunctions are orthogonal if their inner (dot) product is zero. In part D we
computed non-zero inner products, so these states are not orthogonal.

F. From the information given, can you tell which wavefunction has more nodes?

Solution:
NO. This can be made rigorous by scaling the wavefunctions and switching labels around.
Convince yourself that we have insufficient information to make any claims comparing the
nodes of either wavefunction.
G. For each of the following eleven matrices, decide whether the matrix could or could
not represent the Hamiltonian for this system. For matrices that could not be the
Hamiltonian, explain why not.

Solution:

The only condition for a valid Hamiltonian is that it is a Hermitian matrix such that H = H† =
(H∗)T . The matrices that satisfy this requirement are 1, 2, 5, 6, 9, and 11. Matrices 3, 4, 7,
8, and 10 are non–Hermitian.

3. This problem deals with the H¨uckel MO theory of π–

conjugated systems
To answer each question, you will need to construct the H¨uckel MOs for each of the
molecules pictured, divide them into sets of occupied and unoccupied orbitals, and
determine the relevant properties, such as ground state energy, bond order, etc.
Solution:
The arbitrary numbering scheme I will use for this problem is
Let’s build the H¨uckel MO Hamiltonian from the 6 carbon atoms. The differences
between benzene and hexatriene are only connectivity:

We now substitute α and β with the values above and find the eigenvalues of each
Hamiltonian numerically. The eigenvalues of Hbenzene (in eV) are

and the eigenvalues of Hhexatriene are

The ionization potential in this model is simply the energy of the HOMO of the ground
state of each molecule (this is the orbital from which the electron is ejected). Since there
are 6 π–electrons, we can fill the three lowest MOs and the HOMO will be the third
lowest. Therefore, the IP of benzene is 11.9 eV, and the IP of hexatriene is 11.5 eV. and we
conclude that benzene holds its HOMO electrons tighter. Experimental values are 9.24384
± 0.00006 eV and 8.30 ± 0.02 eV, respectively, which agree with the trend predicted by
the H¨uckel theory. What are some reasons the experimental values are systematically
lower in magnitude?

B. Compare the total energies of the two 10-electron conjugated systems below. Which
one is more stable? How do you explain this?

Solution:
This problem is another straightforward application of H¨uckel theory. My numbering
scheme will be
The two H¨uckel Hamiltonians for the cyclic and linear systems are (with zeroes omitted)
Finding the eigenvalues of these Hamiltonians numerically yields (in eV):

The ground state of each molecule has 10 electrons in the first 5 MOs. Summing these
MO energies yields

We predict the cyclic structure to be more stable by roughly 0.8 eV, presumably due to
“aromaticity”.
C. What is the bond order of the selected bond in the molecule below? How do you
rationalize this result in terms of resonance structures?
 Solution:

This molecule is

Note that carbon 7 does not participate in the π network, being completely saturated.
There is no aromatic cyclic structure: the π system runs along carbons 1-2-3-4-5-6. Thus, in
terms of H¨uckel theory, this problem is identical to hexatriene, which we solved above in
part A. I’ve numbered this molecule so that we can use the same Hamiltonian,
Hhexatriene, without needing to permute any rows or columns. However, in this problem,
we are interested in the bond order of the 2-3 bond, thus we will need the normalized
eigenvector for each MO energy eigenvalue. Calculating these with a computer algebra
program yields:
Remember that this is the bond order contribution only from the π–network. The σ–
framework adds an additional bond order, yielding a total bond order ≈ 1.5. It’s useful
to note that the first two MOs are bonding in nature (add positively to the bond order
sum), while the third MO is anti-bonding with respect to carbons 2 and 3 (adds
negatively to the bond order sum). If we were to plot the MOs, we would see a node
between atoms 2 and 3 in the third MO.

In terms of resonance structures, the partial bond order makes sense. We can arrow-
push to form a di-radical species (on 1 and 6) that has a double bond between carbons
2 and 3. The “average” bond order over all resonance structures is then about 1.5, in
agreement with H¨uckel theory.
D. Plot the HOMO and LUMO for each molecule below. Is there anything about these
orbitals that might tell you about the relative degree of conjugation between the pair of
substituents in the meta (left) and para (right) positions?

Solution:
This problem asks us to compare the MOs of two different structural isomers of benzene
with π–conjugated substituents. My numbering scheme is as follows:
There are 10 π–electrons, so the lowest 5 MOs will be filled in the electronic ground state.
The 5th lowest MO is the HOMO and the 6th lowest MO is the LUMO. The eigenvectors
corresponding to
Plotting the approximate wavefunctions for these orbitals gives us:
In each case, the HOMO orbital has a bonding interaction within the substituents and an
antibonding interaction between the substituents and the ring. The LUMO has an anti-
bonding interaction within the substituents and bonding interaction between the
substituents and the ring. Examining the magnitude of the eigenvector elements closely,
we see that the bonding character in the meta substituents is slightly weaker than than in
the para substituents (0.43 × 0.26 = 0.11 < 0.47 × 0.26 = 0.12).

4. It is straightforward to extend H¨uckel Theory to deal with π

systems containing elements other than carbon and hydrogen.

A. First, let us consider including heteroatoms such as nitrogen instead of carbon inside
of conjugated rings. To use the H¨uckel prescription, we simply need α values for C and
N and β values for CC and CN bonds. We already know that α(C) = 11.2 eV and β(CC) = –
0.7 eV . Which of the following possible values for α(N) and β(CN) are most reasonable
and why?
 Solution:

B. Use the parameters you chose in part A to compute the π MOs of pyridine.
Compare your results to what you find for benzene. Do you notice any differences?
What is the partial charge on nitrogen in this approximation? Does this make sense?

Solution:
We build the H¨uckel matrices in the same way as problem 3. Diagonal terms representing
orbital energies on N will use αN , and CN off-diagonal terms will use βCN nearest neighbor
interactions.
 The Hamiltonian for pyridine is

The MO eigen-energies for pyridine are:

Comparing these (and their eigenvectors, not shown) to benzene, we make the following
observations:

1. The lowest energy MO is lower in energy, due to the stronger electronegativity of N.

2. Only one of each pair of degenerate MOs is brought down in energy. This is because
one of each pair has a node through the N atom; in the limits of H¨uckel theory, this
MO will not be affected at all by changes at these sites.
C. We can also use H¨uckel theory to understand how substituents, like a fluorine atom,
will affect the π orbitals. Toward this end, we can assume that a fluorine atom will lower
the average energy of the carbon it is attached to by 0.2 eV. Thus a CH carbon will have
α(C) = -11.2 eV while a CF carbon will have β(C)-11.4 eV . Use this parameterization to
compute the MOs of 1-fluorobenzene. What is the charge on the substituted carbon?

Solution:

We will perform a similar calculation with 1-fluorobenzene. As fluorine deshields the

carbon nucleus, we take αC = -11.4 eV for carbons that have CF bonds. We will assume
β remains the same as for benzene. After building the Hamiltonian matrix and
calculating its eigenvectors, we find the partial charge on the fluorinated carbon to be
-0.11, i.e. the fluorine effectively pulls more electron density onto its C atom

D. You are attempting a partial fluorination of pyridine. You want to selectively

fluorinate two of the carbons, while leaving the others untouched. Which sites will the
fluorines prefer? To answer this question, compute the energies of all six of the
difluorinated isomers below. Which has the lowest energy? How do you rationalize
your result?
Solution:

We now compare the energies of the six possible di-substituted fluorobenzenes. For each,
we build the Hamiltonian matrix, calculate the eigenenergies, occupy these MOs with the 6
π electrons and then sum the one-electron energies of the occupied orbitals to find the
energy of the ground electronic state. The energies (in eV) of the six isomers are:

H¨uckel theory predicts that the 3,5- and 3,4-difluorobenzene compounds will be the most
stable isomers. We could justify this result by noting that these two are the only two isomers
not to have a fluorine atom ortho to the N atom, indicating that the increased π-electron
density associated with fluorinated carbons would interact unfavorably with the increased π–
electron density on the electronegative N.