Hdout Chap 10 5210

CHAPTER 10
SEMIEMPIRICAL METHODS AND APPLICATIONS OF SYMMETRY

OUTLINE
Homework Questions Attached
PART A: The Hckel Model and other Semiempirical Methods

SECT
TOPIC
1.
Hckel Molecular Orbital Model
2.
Application to Ethylene
3.
Application to the Allyl Radical (C3H5)
4.
Electron Charge and Bond Order
5.
Application to Butadiene
6.
Introduction to Heteroatoms
7.
Semiempirical Methods for Sigma Bonded Systems
PART B: Applications of Symmetry

SECT
TOPIC
1.
UV/Visible Absorption Selection Rules
2.
3.
Application to Carbene
4.
Use of Symmetry in Simplifying MO Calculations
5.
Construction of SALCs: Application to the Allyl Radical
6.
Solution to the Allyl Radical Using SALCs
7.
Application to -Bonding in Pyrrole
Chapter 10 Homework
PART A: The Hckel Model and other Semiempirical Methods
1.
Write the Secular determinant for the following molecules in terms of

(i) , and E, (ii) x = (-E)/
In molecules with heteroatoms, check PP slides for appropriate heteroatom
parameters
(a) Square cyclobutadiene
C1
C2
C4
C3
(b) Trimethylenemethane
This is a diradical species.
Ive drawn one of 3 resonance forms
C3
C1
C2
C4
(c) Acrolein
(d) Furan
C1
C2
3.
O4
O5
C4
C1
C3
2.
C3
C2
How many electrons does the oxygen atom in (a) Acrolein, (b) Furan,
contribute to the pi electron system.
C1
C2
C4
C3
Let's consider Cyclobutadiene:

In the solution to Prob. 1 (a), we showed that the secular determinant is:
x
1
0
1
1 0 1
x 1 0
0
1 x 1
0 1 x
With a bit of algebra, it can be shown that the above determinant expands to give:
x4-4x2 = 0
(a) Solve this equation to obtain the 4 energy levels.
Note: Two of the four energies are degenerate.
(b) It can be shown (with a bit more algebra) that the non-normalized
molecular orbitals of cyclobutadiene are:
1 c1 1 2 3 4
2 c1 1 3
3 c2 ( 2 4 )
4 c1 1 2 3 4
Determine the normalized molecular orbitals.

(c) Calculate the total energy and the Delocalization energy.
(d) Calculate the electron charge for each atom.
(e) Calculate the bond order for each bond.
4.
Consider 1,3-butadiene:
C1
C2
C3
C4
Note: The solution to this problem is given in the Chap. 12 PowerPoint presentation.
(a) Write the Secular Determinant.
(b) Solve the Secular Determinant to obtain the 4 energy levels.
(c) Determine the normalized coefficients of the molecular orbitals
corresponding to each energy.
(d) Calculate the total energy and the Delocalization energy.
(e) Calculate the electron charge for each atom.
(f) Calculate the bond order for each bond.
5.
Consider butadiene in the lowest excited state (figure to right).

Note: The energies and orbitals are the same as in the ground state.
(a) Calculate the electron charge on each atom.
E4
E3
(b) Calculate the bond order for each bond.

E2
E1
PART B: Applications of Symmetry
6.
Methylenecyclopropene belongs to the C2V point group.

C2V E
C2 V(xz) V(yz)
A1
A2
B1
B2
1
1
-1
-1
1
1
1
1
1
-1
1
-1
1
-1
-1
1
z
Rz
x, Ry
y, Rx
x2, y2, z2
xy
xz
yz
Shown below are two electronic transitions.

The letter to the left of each orbital is its representation.
For each transition, give:
(i) the representations of the ground state, 0, and
the excited state, i .
(ii) whether or not the transition is allowed.
(iii) if it is allowed, is the transition polarized parallel to or perpendicular to the
the principal axis.
(a)
(b)
b2
b2
a2
a2
a2
b2
b2
b2
b2
b2
b2
b2
b2
b2
b2
a2
7.
Now consider two transitions of the Methylenecyclopropene cation.

For each transition, give:
(i) the representations of the ground state, 0, and
the excited state, i .
(ii) whether or not the transition is allowed.
(iii) if it is allowed, is the transition polarized parallel to or perpendicular to the
the principal axis.
(a)
b2
a2
a2
a2
b2
b2
b2
b2
b2
b2
b2
b2
b2
a2
8.
(b)
b2
b2
Consider trans-1,3-butadiene, which has C2h symmetry. In class (and in the PP

presentation), we solved the 4x4 Secular Determinant to determine the Hckel Energies
and Molecular Orbitals.
C2h
Ag
Bg
Au
Bu
E
1
1
1
1
C2
1
-1
1
-1
i
1
1
-1
-1
h
1
-1
-1
1
x2,y2,z2,xy
xz,yz
z
x,y
H
C
H2C
C
H
CH2
(a) It can be shown that that the pz orbitals, 1, 2, 3 and 4 can be combined
to give 4 SALCs, two belonging to the Bg and two to the Au representation.
Use projection operators to determine the 4 SALCs for butadiene. Normalize the
SALCs.
(b) Determine the 2x2 Secular Determinants corresponding to the Bg and Au
representations.
(c) Solve the 2x2 Secular Determinants to determine the energies and wavefunctions
belonging to the Bg and Au representations.
Chapter 10
Semiempirical Methods and
Applications of Symmetry
Part A: The Hckel Model and other
Semiempirical Methods
Part B: Applications of Symmetry
Slide 1
Part A: The Hckel Model and other Semiempirical

Methods

Introduction of Heteroatoms
Semiempirical methods for sigma bonded systems
Slide 2

Developed by Eric Hckel in 1920s to treat -electron systems.
Extended by Roald Hoffman in 1963 to treat -bonded systems.
The Hckel model has been largely superseded by more accurate
MO calculations. However, it is still useful to obtain qualitative
predictions of bonding and reactivity in conjugated systems.
The model is also very useful in learning how to perform the
Secular Determinant and Molecular Orbital calculations of the
type used in Hartree-Fock theory, but at a much simpler level.
Slide 3
Assumptions
1. The and electrons are independent of each other.
The electrons move in the constant electrostatic potential
created by the electrons.
2. The carbons are sp2 hybridized.
The remaining pz orbital is perpendicular to the molecular
framework.
3. The electron Molecular Orbitals are linear combinations of
the pz orbitals (i).
4. The total electron Hamiltonian is a simple sum of effective

one electron Hamiltonians.
Slide 4
Linear Equations and Secular Determinant

+
Variational Method
One has N equations, where

N is the number of carbon atoms.
Slide 5
Additional Assumptions
5. The Orbitals are Normalized:
Sii = 1
The overlap between orbitals is 0: Sij = 0 (ij)

6. The diagonal Hamiltonian elements are given by
an empirical parameter,
7. Off-diagonal Hamiltonian elements are given by
an empirical parameter, , if the carbons are adjacent
Hij = : Adjacent Carbons
Hij = 0: Non-Adjacent Carbons
Note: <0 and <0
Slide 6
Parameter Values
What is the value of ?
Who cares?
cancels out in almost all applications, such as transition or
reaction energies.
What is the value of ?
Who knows?
Estimates of the best value of vary all over the place.
As noted in the text, values ranging from 30 kcal/mol to -70 kcal/mol
( -130 to -290 kJ/mol) have been used.
For lack of anything better, well use = -200 kJ/mol.
Slide 7

Methods

Slide 8
Application to Ethylene (C2H4)

Secular Determinant and Energies
Put in Hckel matrix elements
Divide all terms

by and define x by
Slide 9
Slide 10
Molecular Orbitals
or
Slide 11
Normalization:
Note: For Hckel calculations, the normalization

condition is always:
Slide 12
Bonding Orbital
Antibonding Orbital
Slide 13
C1
C2
Electrons are not delocalized in 2
C1
C2
Electrons are delocalized in 1
Slide 14

Methods

Slide 15
The Allyl radical has 3 electrons
Slide 16
Divide by
Define
on
Board
Slide 17
Normalization
Normalization
Slide 18
Normalization
Slide 19
Wavefunction Check
You can always check to be sure that youve calculated the
wavefunction correctly by calculating the expectation value
of E and see if it matches your original calculated value.
Well illustrate with 3.
It checks!!
Slide 20
10
C1
C2
C3
C1
C2
C3
C1
C2
C3
Slide 21
Delocalization Energy
The delocalization energy is the total electron energy relative to the
energy of the system with localized bonds.
Slide 22
11

Methods

Slide 23

Electron Charge (aka Charge Density)
The electron charge on atom is defined by:
ci is the coefficient of the ith. MO on atom .
Bond Order
The bond order between atoms and is defined by:
Slide 24
12
Application to the Allyl Radical

Electron Charge:
Bond Order:
Slide 25

Methods

Slide 26
13
1,3-Butadiene has 4 electrons
Note: Application of the Hckel theory to Butadiene is one of your

HW problems.
The solution is worked out in detail below. I will
just outline the solution.
Divide by
Define
Slide 27
Slide 28
14
Slide 29
Butadiene Delocalization Energy
The additional stabilization of butadiene

compared to 2 ethylenes is a result of
electron delocalization between the
two double bonds.
Slide 30
15
Butadiene Wavefunctions
From first equation:

From second equation:
From fourth equation:
Slide 31
Normalization:
(because all overlap integrals are 0)
It is straightforward to perform the same procedure to determine

2 , 3 and 4.
The results are shown on the next slide.
Slide 32
16
C1
C2
C3
C4
C1
C2
C3
C4
C1
C2
C3
C4
C1
C2
C3
C4
Slide 33
Butadiene: Electron Charge and Bond Order
Electron Charge:
Actually, Butadiene (and the Allyl radical) belong to a class of

hydrocarbons called Alternant hydrocarbons, for which all qi = 1.0
All straight-chain polyalkenes are alternant hydrocarbons.
Slide 34
17
Bond Order:
Note: For a full bond, p = 1.

For a pure bond, p = 0.
Therefore, the above bond orders reveal that the bonds between
C1-C2 and C3-C4 are not as strong as in ethylene.
p23 > 0 shows that there is significant character in the
C2-C3 bond.
Slide 35

Methods

Slide 36
18
Introduction of a heteroatom such as N or O into a conjugated
system requires different values of and than those used for
Carbon because the heteroatom has a different electronegativity;
i.e.Eneg(C) < Eneg(N) <Eneg(O).
It is useful to put the new values of the Coulomb and Resonance Integrals,
X and X (where X is the heteroatom), in terms of the original and .
The forms that is generally used are:
and
where hX and kX are constants that depend upon the heteroatom.
Slide 37
Atom
hX
Bond
kX
0.5
1.0
1.5
0.8
2.0
0.8
1.0
1.0
2.0
0.4
Slide 38
19
A heteroatom can donate different numbers of electrons into the

electrons depending upon its bonding.
Example: Nitrogen has 5 valence electrons
In pyridine, 4 of the 5 valence electrons are involved in

(a) 2 bonds and (b) 2 electrons in the lone pair.
Therefore, this nitrogen will donate only 1 electron.
In pyrrole, 3 of the electrons will be involved in bonds.

This nitrogen will donate 2 electrons.
Slide 39
Example: Bonding in Pyrrole

This will illustrate how a heteroatom is handled in the
Hckel Molecular Orbital Model.
For pyrrole, 2 electrons are donated to the system.

The heteroatom parameters are: hN = 1.5 and kN = 0.8
Therefore:
Slide 40
20
The Secular Determinant
Slide 41
This is a 5x5 Secular Determinant, which can be expanded to yield

a fifth order polynomial equation, which can be solved to give:
(a) five values of x.
(b) five energies.
(c) five sets of coefficients.
But, Im just really not in the mood right now.
Howsabout I just give you the results?
No Applause, PLEASE !!!
Slide 42
21
Wavefunctions and Energies
Note: There are 6 electrons.

Count them.
Note: Actually, I used symmetry to simplify
the 5x5 determinant into a 2x2 and a
3x3 determinant
Ill show you how at the end of
the chapter.
Slide 43
Electron Charge
Electron Charge:
Slide 44
22
Bond Order
Bond Order:
Slide 45

Methods

Slide 46
23
Semiempirical Methods for Sigma Bonded Systems

The Hckel model was developed to treat only bond systems.
A number of methods have been developed to treat systems with
bonded molecules as well as molecules with both and bonds.
Three of the most popular are: (1) Pariser-Pople-Parr (PPP) Model
(2) The Extended Hckel model
(3) MNDO methods
We will discuss each method qualitatively.
Slide 47
Pariser-Pople-Parr (PPP) Model

The Hckel Model neglects repulsion between electron.
The PPP Model introduces interelectron repulsion into the
effective Hamiltonian:
HPPP = HHckel + HRepulsion
The inclusion of HRepulsion introduces Coulomb Integrals into
the expression for the Energy.
However, these integrals are not calculated.
They are represented by empirical parameters.
Slide 48
24
The Extended Hckel Model

As the title suggests, this is an extension of the Hckel Model to treat
bonded molecules, developed by Roald Hoffmann (in 1963).
The concept is the same in that one assumes that:
1. The Molecular Orbitals are linear combinations of atomic
orbitals (i).
2. The total Hamiltonian is a simple sum of effective
one electron Hamiltonians.
3. If one applies the variational principle, then a Secular Determinant

is obtained.
Slide 49
3. The orbitals for Core shell electrons are ignored. Valence shell
atomic orbitals are given by STOs; e.g. 2s, 2px, 2py, 2pz
4. The parameters in the Secular Determinant are determined
as follows:
Overlap integrals, Sij are calculated directly (unlike

the Hckel model where they are assumed to be zero)
Coulomb Integrals, Hii, are set equal to the negative

of the valence shell ionization energies.
Resonance Integrals, Hij, are calculate with the

Wolfsberg-Helmholtz formula
Slide 50
25
MNDO Methods
An ab initio Hartree-Fock calculation on a molecule requires
the calculation of ~b4/8 integrals.
If one uses a high level basis set on a medium size molecule
(10-20 atoms), a typical number of basis functions might be
b=400, resulting in ~3x109 integrals.
A very great percentage of the time required for a Hartree-Fock
calculation is in the evaluation of these integrals.
There have been a number of semiempirical methods developed
which approximate these integrals. The most popular of these
methods is the MNDO (Modified Neglect of Differential Overlap)
series of methods developed by M. J. S. Dewar.
Ill comment briefly on them.
Slide 51
Assumptions:
Core (inner shell) electrons are not treated explicitly.
An empirical core-core repulsion term is introduced.
A minimal basis set with single ns, npx, npy, npz atomic
orbitals is used to represent valence shell electrons.
Overlap integrals are neglected.
The one-center and two-center integrals are either
ignored or approximated by empirical parameters.
The empirical parameters are obtained by finding the values
that give the best agreement with experimental data;
i.e. Heats of Formation, Ionization Energies, Dipole Moments,etc.
Slide 52
26
The three different MNDO methods are:

MNDO: The original of the methods. In general, this is not
as accurate as later methods.
AM1: This stands for Austin Model 1
Dewar had moved to UT-Austin and wanted to give
credit to his new university.
This method improves upon the parameterization of
the integrals.
PM3: This stands for Parametric Method 3
This improves the parameterization method still further.
Slide 53
Because the integrals are determined empirically, and are not

calculated, MNDO methods are thousands of times as fast
as ab initio calculations.
The results are generally not as accurate as ab initio calculations,
but the MNDO methods are good for:
(a) Semi-quantitative results.
(b) Calculations on very large molecules, where
ab initio calculations are not feasible.
Slide 54
27
Chapter 10
Semiempirical Methods and
Applications of Symmetry
Slide 1

Solution to the Allyl Radical using SALCs
Slide 2
Spectroscopic Selection Rules

When light (of frequency ) is shined on a sample, the lights
electric vector interacts with the molecules dipole moment, which
adds a perturbation to the molecular Hamiltonian.
The perturbation mixes the ground state wavefunction (0) with

various excited states (i). A simpler way to say this is that the
light causes transitions between the ground state and the excited
states.
Consider a transition between the ground state (0) and the
ith. excited state (i).
Time dependent perturbation theory can be used to show that
the intensity of the absorption is proportional to the square
of the transition moment, M0i.
Slide 3
The transition moment is:

^ is the dipole moment operator:
Thus, the transition moment has x, y and z components.

Slide 4
Selection Rules for UV/Vis Absorption Spectra

Lets use Group Theory to predict whether specific electronic transitions
in some molecules can be excited by the absorption of UV radiation.
We want to determine whether the components of the transition
moment are nonzero.
A question which must be resolved is how to determine the

representation of the overall electronic wavefunction ( both 0 and i )
from the representations of the individual MOs.
However, first lets take a short detour to briefly discuss
spin-forbidden transitions.
Slide 5
Spin Forbidden Transitions

When considering electronic transitions (i.e. UV and Vis. Spectroscopy),
the total wavefunction is actually the product of a spatial function and
a spin wavefunction.
It can be shown that spin wavefunctions corresponding to different

values of S are orthogonal:
Therefore, the transition moment is zero unless the total spin
quantum number is conserved; e.g. Singlet Triplet transitions
are forbidden.
Slide 6
Note that I left the spins paired in the excited state (i.e. this is the
singlet form of the excited state).
Thats because, as we just saw, absorptions involving a change
in spin multiplicity are spin forbidden.
How do we get the representations, (0) and (i), from the
individual is of the MOs?
Its easy!! The representation of the total wavefunction is the direct
product of the representations of all MOs with 1 or 2 electrons (we count
the representation twice when the orbital has 2 electrons)
Slide 7
If the ground state contains only doubly occupied orbitals, then

it belongs to the totally symmetric representation.
All doubly occupied orbitals can be ignored when determining
the representation of an excited electronic state.
Note: It is conventional to use small letters (e.g. a1g) to characterize
the representation of individual MOs and large capital letters (e.g. A1g)
to characterize the representation of the total wavefunction.
Slide 8

Slide 9
C2h E
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
Trans 1,3-butadiene belongs to the C2h point group.

The four Hckel orbitals were developed in earlier in this chapter.
Slide 10
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
(1) 1
-1
-1
au
(2) 1
-1
-1
bg
(3) 1
-1
-1
au
(4) 1
-1
-1
bg
C2h E
C1
C2
C3
C3
C4
C4
Energy
C1
C2
C1
C2
C3
C1
C2
C3
C4
C4
Slide 11
C2h E
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
x,y
Lets consider a couple of butadiene * transitions.
Therefore, this transition is labelled: Ag Bu

Note that the transition is labelled by the symmetries of the total
wavefunctions, and not the symmetries of the individual MOs involved.
Slide 12
Polarization of Electronic Transitions

C2h E
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
x,y
Note that M0iz = 0.

Consider a single crystal of butadiene
(not likely for this molecule)
If incoming light is polarized along the z-axis (C2),
it will not be absorbed.
Therefore, the polarization of this transition is Perpendicular
Slide 13
C2h E
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
x,y
Lets consider a second butadiene * transition.
Therefore, this transition is labelled: Ag Ag
Therefore, this is not an allowed transition.

Slide 14
C2h E
C2
Ag
Bg
-1
-1
Au
-1
-1
Bu
-1
-1
x,y
Back to: Ag Bu
You may have learned a shortcut in another course.
Shortcut: If the representation of the excited state is the same as
x, y, or z, the transition is allowed.
Corky: Shortcuts are Nice!!!
Mookie: Thats right, Corkster, except when they dont work.
Like on tests!!!
Slide 15

Slide 16
Carbene UV Selection Rules

Carbene: 8 electrons
C2V symmetry
Triplet GS
b2
a1
b1
z
a1
x
b2
We will consider only

transitions arising from
the a1 and b1 frontier
orbitals.
a1
a1
Slide 17
b2
b2
C2V
C2 V(xz) V(yz)
a1
a1
A1
b1
b1
A2
-1
-1
B1
-1
-1
a1
a1
B2
-1
-1
Therefore, the overall transition is: B1 A1
This transition is allowed and is polarized perpendicular to the principal axis.

Slide 18
b2
b2
C2V
C2 V(xz) V(yz)
a1
a1
A1
b1
b1
A2
-1
-1
B1
-1
-1
a1
a1
B2
-1
-1
Therefore, this transition is labelled: B1 A1

This transition is allowed and is polarized perpendicular to the principal axis.
Corky: Right!! And the shortcut also predicts that the transition is allowed
because the excited state representation (A1) is the same as z
Mookie: But the shortcut predicts the wrong polarization.
Corky: Well, half right aint bad!!
Mookie: Oy Vey!!
Slide 19
b2
b2
C2V
C2 V(xz) V(yz)
a1
a1
A1
b1
b1
A2
-1
-1
B1
-1
-1
a1
a1
B2
-1
-1
Overall Transition: B1 A2
Mookie: Okay, Corky, go ahead and use the shortcut.
Corky: Well, the excited state belongs to A2. Since none of x, y, or z
is A2, the transition is forbidden. Piece of Cake!!
Mookie: If you dont mind, Ill work it the long way just to make sure.
Slide 20
10
b2
b2
C2V
C2 V(xz) V(yz)
a1
a1
A1
b1
b1
A2
-1
-1
B1
-1
-1
a1
a1
B2
-1
-1
Overall Transition: B1 A2
The shortcut predicts that this is a forbidden transition.

Actually it is allowed and is polarized perpendicular to the principal axis.
Mookie: So, Corky. What do you think of your shortcut now??
Corky: Huh? Waddya Say?
I didnt hear a thing you said. I was watching Survivor.
Slide 21

Slide 22
11
Use of Symmetry in MO Calculations

The molecular orbitals of a molecule must belong to
(i.e. transform as) one of the irreducible representations of the
point group to which the molecule belongs.
If instead of using the original atomic orbitals,If you perform a
calculation with Symmetry Adapted Linear Combinations (SALCs)
which belong to representations of the molecules point group,
the calculation is simplified.
Consider, for example, using SALCs, Si, of the original atomic
orbitals:
The A1 and B1 in brackets are the
representations to which each Si belongs.
Slide 23
It can be shown from Group Theory that if one forms the Secular
Determinant by using matrix elements of the Si rather than i,
then the Determinant is Block Diagonalized
Lets say that i belongs to i and j belongs to j.
Remember that the Hamiltonian belongs to A1 (A1g etc)
Then the Hamiltonian matrix element is :
This integral is non-zero only if the Direct Product is:
As we learned in Chapter 5, this is true only if i = j ;

i.e. if the two SALCs, Si and Sj belong to the same representation.
Slide 24
12
Lets say that a system has four SALCs, with two belonging to
the A1 and two to the B1 representation. Then the 4x4 Secular
Determinant will be Block Diagonalized, as follows:
It can be further shown that if a Secular Determinant is

block diagonalized, then one break the determinant down into
smaller determinants.
and
Thus, a 4x4 Secular Determinant, which requires solution
of a 4th. order polynomial, has been simplified into two
2x2 Secular Determinants, which can be solved more easily.
Slide 25

Slide 26
13
Construction of SALCs
As discussed above, if Symmetry Adapted Linear Combinations (SALCs)
of atomic orbitals are used instead of the orbitals themselves,
then there is a significant simplification of the Secular Determinant.
In this section, we are going to learn:
(a) How to determine the number of SALCs of each of the irreducible
representations of the point group that can be formed from an
equivalent set of atomic orbitals.
(b) How to generate the SALCs
We will demonstrate these methods on the Allyl Radical,
which has C2V symmetry.
Slide 27
One can calculate the number of each type of irreducible representation

(e.g. A1, A2, ...) are contained in a reducible representation formed from
a set of equivalent Atomic Orbitals.
The required formula (derived from the Great Orthogonality Theorem)
is:
In this formula:
(a) R refers to one of the symmetry operations of the group.
(b) h is the order of the group (the number of symm. operations.
(c) Trred(R) is the Trace (or Character) corresponding to operation
R in the reduced representation.
(d) Trj(R) is the Trace (or Character) corresponding to to operation
R in the jth. irreducible representation.
(e) nj is the number of times that the jth. irreducible representation
appears in the reducible representation
Note: The text uses the more common symbol, , to represent the
character (or trace). However, were already using to
represent atomic orbitals.
Slide 28
14
SALCs of the Allyl Radical

C2V E
C2 V(xz) V(yz)
A1
A2
-1
-1
B1
-1
-1
B2
-1
-1
The 3 atomic pz orbitals will form the basis for the

reducible representation.
To form the reducible representation, Red, one performs each
symmetry operation.
If the orbital is unchanged, it contributes +1 to Tr(R)
If the orbital changes sign, it contributes -1 to Tr(R)
If the orbital moves to a new atom, it contributes 0 to Tr(R)
Slide 29
C2V E
C2 V(xz) V(yz)
A1
A2
-1
-1
B1
-1
-1
B2
-1
-1
When E is applied, all 3 orbitals are unchanged: Red(E) = +3

When C2 is applied, 1 and 3 exchange, 2 changes sign: Red(C2) = -1
When V is applied, all 3 change sign: Red(V) = -3
When V is applied, 1 and 3 exchange, 2 is unchanged: Red(V) = +1
Slide 30
15
h=4 C2V E
A1
A2
B1
B2
1
1
1
1
Red +3
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
-1
-3
+1
Generate the number of times each representation appears in Red
Slide 31
Construction of the SALCs
One uses a projection operator:
C2V E
1
A1
A2
1
B1
1
1
B2
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
Red +3
-1
-3
+1
R(i) represents the result of operating on a (arbitrary) atomic orbital.

Trj(R) is the trace of the jth irreducible representation for operation R
N is the normalization constant
Slide 32
16
C2V E
1
A1
1
A2
B1
1
1
B2
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
Red +3
-1
-3
+1
A2 SALC
Well use 1 to generate the SALC
Normalized:
Slide 33
Lets demonstrate that S1 belongs to

the A2 representation.
C2V E
1
A1
A2
1
B1
1
B2
1
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
Red +3
-1
-3
+1
The signs on the transformed values of S1 match those of the A2

representation.
Slide 34
17
C2V E
1
A1
1
A2
B1
1
1
B2
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
Red +3
-1
-3
+1
B2 SALCs
Well use 1 to generate the first SALC
Normalized:
Slide 35
C2V E
1
A1
A2
1
B1
1
B2
1
C2 V(xz) V(yz)
1
1
1
1
-1
-1
-1
1
-1
-1
-1
1
Red +3
-1
-3
+1
B2 SALCs
Well use 2 to generate the second SALC
Normalized:
Slide 36
18

Slide 37
Solution for the Allyl Radical Using SALCs
Allyl belongs to the C2V point group.

The plane of the molecule is the x-y plane.
The SALCs are:
In this section, we will use the above SALCs to derive the energy
levels and molecular orbitals in the Allyl radical.
Slide 38
19
The Allyl Secular Determinant using Symmetry
Matrix Elements
Slide 39
Matrix Elements (Contd.)
Slide 40
20
A2
block
A2
block
Divide by
Define
B2
block
B2
block
A2 Block
Slide 41
A2
block
B2 Block
B2
block
B2 Wavefunctions
Similarly
Slide 42
21
Allyl with Symmetry: Summary

A2
block
B2
block
A2 Block
B2 Block
Slide 43

Slide 44
22
Example: Bonding in Pyrrole

This will illustrate how a heteroatom is handled as well as provide
another example of the use of symmetry.
The calculations are worked out in detail in the slides below.
Ill just outline the procedure (relatively quickly), but the slides will
provide you with another worked out example.
For pyrrole, 2 electrons are donated to the system.

The heteroatom parameters are: hN = 1.5 and kN = 0.8
Therefore:
Slide 45
E
A partial Character Table
for the C2V point group is:
C2 V(xz) V(yz)
A2 1
-1
-1
B2 1
-1
-1
The 5 SALCs belong to the A2 and B2 representations.
Well demonstrate (on the board) that Sa belongs to the A2

and Sc to the B2 representation.
Slide 46
23
A2 Block
Slide 47
A2 Block
Slide 48
24
A2 Block
where
I will name the energies Er, Es, ... so that I can renumber them
according to order of increasing energy at the end of the problem.
Slide 49
A2 Block
Wavefunctions
Normalization:
Slide 50
25
A2 Block
Analogously
Slide 51
B2 Block
Slide 52
26
B2 Block
Slide 53
B2 Block
Slide 54
27
B2 Block
where
Reduces to
Slide 55
B2 Block
This cubic equation can be solved numerically to yield the roots,

x = -2.320, -1.189, +1.008
Remember that were initially naming our roots (and wavefunctions)
r, s (A2) and t, u, v (B2). Well put them in numerical order according
to increasing energy at the end.
Slide 56
28
B2 Block
Wavefunctions
+
From Second Eqn.
From Third Eqn.
Slide 57
B2 Block
Normalization:
Analogously
Analogously
Slide 58
29
Wavefunctions and Energies
Slide 59
30

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CHAPTER 10

SEMIEMPIRICAL METHODS AND APPLICATIONS OF SYMMETRY

PART A: The Hckel Model and other Semiempirical Methods

Hckel Molecular Orbital Model

Application to the Allyl Radical (C3H5)

Electron Charge and Bond Order

Semiempirical Methods for Sigma Bonded Systems

PART B: Applications of Symmetry

UV/Visible Absorption Selection Rules

Use of Symmetry in Simplifying MO Calculations

Construction of SALCs: Application to the Allyl Radical

Solution to the Allyl Radical Using SALCs

Application to -Bonding in Pyrrole

Write the Secular determinant for the following molecules in terms of

Let's consider Cyclobutadiene:

Determine the normalized molecular orbitals.

Consider butadiene in the lowest excited state (figure to right).

(b) Calculate the bond order for each bond.

PART B: Applications of Symmetry

Methylenecyclopropene belongs to the C2V point group.

Shown below are two electronic transitions.

Now consider two transitions of the Methylenecyclopropene cation.

Consider trans-1,3-butadiene, which has C2h symmetry. In class (and in the PP

Part A: The Hckel Model and other Semiempirical

Hckel Molecular Orbital Model

Hckel Molecular Orbital Model

4. The total electron Hamiltonian is a simple sum of effective

Linear Equations and Secular Determinant

One has N equations, where

5. The Orbitals are Normalized:

The overlap between orbitals is 0: Sij = 0 (ij)

Part A: The Hckel Model and other Semiempirical

Hckel Molecular Orbital Model

Application to Ethylene (C2H4)

Put in Hckel matrix elements

Divide all terms

Note: For Hckel calculations, the normalization

Electrons are not delocalized in 2

Electrons are delocalized in 1

Part A: The Hckel Model and other Semiempirical

Hckel Molecular Orbital Model

Application to the Allyl Radical (C3H5)

The Allyl radical has 3 electrons

Secular Determinant and Energies

Part A: The Hckel Model and other Semiempirical

Hckel Molecular Orbital Model

Electron Charge and Bond Order

ci is the coefficient of the ith. MO on atom .

Application to the Allyl Radical

Part A: The Hckel Model and other Semiempirical

Hckel Molecular Orbital Model

Note: Application of the Hckel theory to Butadiene is one of your

Secular Determinant and Energies

Butadiene Delocalization Energy

The additional stabilization of butadiene

From first equation:

(because all overlap integrals are 0)

It is straightforward to perform the same procedure to determine